Boosting elimination of sunscreen, Tetrahydroxybenzophenone (BP-2), from water using monopersulfate activated by thorny NanoBox of Co@C prepared via the engineered etching strategy: A comparative and mechanistic investigation.

As sunscreens, benzophenones (BPs), are regarded as emerging contaminants, most of studies are focused on removal of 2-hydroxy-4-methoxybenzophenone (BP-3), which, however, has been employed for protecting skin. Another major class of BPs, which is used to prevent UV-induce degradation in various products, is completely neglected. Thus, this present study aims to develop a useful advanced oxidation process (AOP) for the first time to eliminate such a class of BP sunscreens from contaminated water. Specifically, 2,2',4,4'-Tetrahydroxybenzophenone (BP-2) would be focused here as BP-2 is intensively used in perfumes, lipsticks, and plastics for preventing the UV-induced degradation. As monopersulfate (MPS)-based AOP is practical for degrading emerging contaminants, a facile nanostructured cobalt-based material is then developed for maximizing catalytic activities of MPS activation by immobilizing Co nanoparticles onto carbon substrates. In particular, ZIF-67 is employed as a template, followed by the etching and carbonization treatments to afford the thorny nanobox of Co@C (TNBCC) with the hollow-nanostructure. In comparison to the solid (non-hollow) nanocube of Co@C (NCCC) from the direct carbonization of ZIF-67, TNBCC possesses not only the excellent textural features, but also superior electrochemical properties and highly reactive surfaces, making TNBCC exhibit the significantly higher catalytic activity than NCCC as well as Co3O4 in activating MPS to degrade BP-2. Mechanisms of BP-2 degradation are also elucidated and ascribed to both radical and non-radical routes. These advantageous features make TNBCC a useful catalyst of activating MPS in BP-2 degradation.

Templating agent-mediated Cobalt oxide encapsulated in Mesoporous silica as an efficient oxone activator for elimination of toxic anionic azo dye in water: Mechanistic and DFT-assisted investigations.

While Azorubin S (AZRS) is extensively used as a reddish anionic azo dye for textiles and an alimentary colorant in food, AZRS is mutagenic/carcinogenic, and it shall be removed from dye-containing wastewaters. In view of advantages of SO4•--related chemical oxidation technology, oxone (KHSO5) would an ideal source of SO4•- for degrading AZRS, and heterogeneous Co3O4-based catalysts is required and shall be developed for activating oxone. Herein, a facile protocol is proposed for fabricating mesoporous silica (MS)-confined Co3O4 by a templating agent-mediated dry-grinding procedure. As the templating agent retained inside the ordered pores of MS (before calcination) would facilitate insertion and dispersion of Co ions into pores, the resulting Co3O4 nanoparticles (NPs) would be grown and confined within the pores of MS after calcination, affording Co@MS. On the contrary, another analogue, Co/MS, is also prepared using the similar protocol without the templating agent-mediated introduction of Co, but Co3O4 NPs seriously aggregate as clusters on MS. Therefore, Co@MS outperforms Co/MS for activating oxone to eliminate AZRS. Co@MS shows a noticeably lower activation energy of AZRS elimination than the existing catalysts, revealing its advantage over the reported catalysts. Moreover, the mechanistic investigation of AZRS elimination by Co@MS-activated oxone has been also elucidated for identifying the presence of SO4•‒, •OH, and 1O2 in AZRS degradation using scavengers, electron paramagnetic resonance spectroscopy, and semi-quantification. The AZRS decomposition pathway is also investigated and unveiled in details via the DFT calculation. These results validate that Co@MS appears as a superior catalyst of oxone activation for AZRS degradation.

Understanding the intermediates and carbon dioxide adsorption of potassium chloride-incorporated graphitic carbon nitride with tailoring melamine and urea as precursors.

In this study, we demonstrated the synthesis of potassium chloride (KCl)-incorporated graphitic carbon nitride, (g-C3N4, CN) with varying amounts of N-vacancies and pyridinic-N as well as enhanced Lewis basicity, via a single-step thermal polymerization by tailoring the precursors of melamine and urea for carbon oxide (CO2) capture. Melamine, as a precursor, undergoes a phase transformation into melam and triazine-rich g-C3N4, whereas the addition of urea polymerizes the mixture to form melem and heptazine-rich g-C3N4 (CN11). Owing to the abundance of pyridinic-N and the high surface area, CN11 adsorbed higher amounts of CO2 (44.52 µmol m-2 at 25 °C and 1 bar of CO2) than those reported for other template-free carbon materials. Spectroscopic analysis revealed that the enhanced CO2 adsorption is due to the presence of pyridinic-N and Lewis basic sites on the surface. The intermediates of CO2adsorption, including carbonate and bicarbonate species, attached to the CN samples were identified using in-situ Fourier-transform infrared spectroscopy (FTIR). This work provides insights into the mechanism of CO2 adsorption by comparing the structural features of the synthesized KCl-incorporated g-C3N4 samples. CN11, with an excellent CO2 uptake capacity, is viewed as a promising candidate for CO2 capture and storage.

Ag-modified TiO2/SiO2/Fe3O4 sphere with core-shell structure for photo-assisted reduction of 4-nitrophenol.

Nitrogen-containing contaminants, such as 4-nitrophenol (4-NP), cause detrimental effects when discharged into the environment and thus should be reduced or removed from ecosystems. In this study, an Ag-loaded TiO2-SiO2-Fe3O4 (TSF) with a core-shell structure was employed for the photo-assisted reduction of 4-NP. Fe3O4, SiO2, and TiO2 in the core-shell structure served as a magnetic center, protective layer, and light absorber, respectively. To improve the reduction activity of 4-NP, Ag was loaded onto TSF under stirring, with a variation of the temperature (2-130 °C) and reaction time (1, 2, and 4 h). Under the optimized conditions, 5Ag-TSF (with 5 wt% of Ag) could promote the reduction of aqueous 4-NP solution (2 × 10-4 M, 75 mL) in the presence of NaBH4 (0.1 M, 5 mL) under irradiation by a metal halide lamp, affording over 98% reduction within 5 min and a rate constant of 0.185 min-1, demonstrating its promising activity. Moreover, due to the advantages of the core-shell structure, the magnetic properties of Fe3O4 were sufficient to enable facile recycling of the sample for further reaction; SiO2 could protect the Fe3O4 center from oxidation or reduction; TiO2 enabled Ag accommodation and absorbed light to generate electron-hole pairs. In summary, an Ag-loaded TiO2-SiO2-Fe3O4 sphere with high activity and recyclability for 4-NP reduction was prepared via a facile and simple stirring method, where the sample can be used as a promising material in environmental remediation.

Detection of Fe3+ and Hg2+ ions through photoluminescence quenching of carbon dots derived from urea and bitter tea oil residue.

In this study, we prepared nitrogen-doped carbon dots (xNCDs) using hydrothermally-treated bitter tea oil residue with urea for the detection of metal ions by monitoring the photoluminescence quenching. The quantum yields of the xNCDs increased from approximately 3.85% (CDs) to 5.5% (3NCDs) and 7.2% (1NCDs), revealing that nitrogen doping effectively increases the fluorescence emission. The increased emission of the xNCDs can be attributed to radiative recombination resulting from the π-π* transition of the C=C or the n-π* transition between the C=O or N=O of sp3 units. Moreover, the CDs have abundant surface-attached phenolic and hydroxyl groups that coordinate with Fe3+ ions and quench the fluorescence. Conversely, Hg2+ ions preferentially adsorb on nitrogen-containing groups, such as amide-carbonyl groups (O=C-NH2) and pyridinic and pyrrolic functionalities, on the surface of the NCDs owing to their strong affinity, quenching the substantial photoluminescence emissions. Our results suggest that bitter tea oil residue-derived carbon dots can be used to selectively detect metal ions, such as Fe3+ and Hg2+, by doping with nitrogen using urea as a nitrogen precursor.

Nanoneedle-Assembled Copper/Cobalt sulfides on nickel foam as an enhanced 3D hierarchical catalyst to activate monopersulfate for Rhodamine b degradation.

While metal oxides are conventionally proposed for activating monopersulfate (MPS) to degrade refractory contaminants, metal sulfides have recently gained increased attention for MPS activation because these sulfides exhibit more reactive redox characteristics to enhance the catalytic activation of MPS. The present study attempts to develop a novel material comprised of metal sulfides with 3D hierarchical nanostructures to activate MPS. Specifically, a 3D hierarchically structured catalyst was fabricated by growing CuCo-layered double hydroxide (LDH) on nickel foam (NF), followed by direct sulfurization, affording Cu/CoS@NF (CCSNF). CCSNF could exhibit a unique morphology of floral bunches comprised of nano-needles, residing on the NF surfaces. Compared with its precursor, CuCo-LDH@NF, oxide analogue, and CuCo2O4@NF, CCSNF possessed superior physical and chemical properties, including larger surface area and pore volume, higher current density, and lower charge transfer resistance. These features render CCSNF a much more effective catalyst than CuCo-LDH@NF and CuCo2O4@NF for activating MPS to degrade Rhodamine B (RB). In particular, RB degradation by CCSNF-activated MPS required an activation energy only 26.8 kJ/mol, which is much lower than the reported values. The activation mechanism and degradation pathway of RB degradation by CCSNF-activated MPS were investigated and validated through experimental evidences and density function theory calculations.

Ultrafine cobalt nanoparticle-embedded leaf-like hollow N-doped carbon as an enhanced catalyst for activating monopersulfate to degrade phenol.

While cobalt (Co) stands out as the most effective non-precious metal for activating monopersulfate (MPS) to degrade organic pollutants, Co nanoparticles (NPs) are easily aggregated, losing their activities. As many efforts have attempted to immobilize Co NPs on supports/substrates to minimize the aggregation issue, recently hollow-structured carbon-based materials (HSCMs) have been regarded as promising supports owing to their distinct physical and chemical properties. Herein, in this study, a special HSCM is developed by using a special type of ZIF (i.e., ZIF-L) as a precursor. Through one-step chemical etching with tannic acid (TA), the resultant product still remains leaf-like morphology of pristine ZIF-L but the inner part of this product becomes hollow, which is subsequently transformed to ultrafine Co-NP embedded hollow-structured N-doped carbon (CoHNC) via pyrolysis. Interestingly, CoHNC exhibits superior catalytic activities than CoNC (without hollow structure) and the commercial Co3O4 NPs for activating MPS to degrade phenol. The Ea value of phenol degradation by CoHNC + MPS was determined as 44.3 kJ/mol. Besides, CoHNC is also capable of effectively activating MPS to degrade phenol over multiple-cycles without any significant changes of catalytic activities, indicating that CoHNC is a promising heterogeneous catalyst for activating MPS to degrade organic pollutants in water.

Assessing nickel oxide electrocatalysts incorporating diamines and having improved oxygen evolution activity using operando UV/visible and X-ray absorption spectroscopy.

The electrolysis of water using renewable energy is a promising approach to developing a sustainable hydrogen-based economy. To improve the efficiency of this process, it will be necessary to develop highly active electrocatalysts that promote the oxygen evolution reaction (OER). In the present study, the OER activity of a nickel oxide electrocatalyst was dramatically improved following the addition of a diamine to the electrolyte solution during electrodeposition. Operando UV/vis absorption spectroscopy was used to assess a number of nickel catalysts containing various diamines and other organic compounds. The data indicate that Ni(II) complexes were formed with the diamines during electrodeposition. Consequently, the catalytic activity of these materials was enhanced based on increased concentrations of active reaction sites for the OER process. Ni K-edge X-ray absorption spectra showed that these catalysts were composed of γ-NiOOH with a Ni3.6+ valence state. The coordination of the diamine molecules to the γ-NiOOH produced structural distortion that contributed to improved OER activity. This structural distortion is likely the most important factor in enhancing the OER activity of inorganic-organic composite catalysts.

Hierarchical ZIF-decorated nanoflower-covered 3-dimensional foam for enhanced catalytic reduction of nitrogen-containing contaminants.

Metal Organic Frameworks (MOFs) represent a promising class of metallic catalysts for reduction of nitrogen-containing contaminants (NCCs), such as 4-nitrophenol (4-NP). Nevertheless, most researches involving MOFs for 4-NP reduction employ noble metals in the form of fine powders, making these powdered noble metal-based MOFs impractical and inconvenient for realistic applications. Thus, it would be critical to develop non-noble-metal MOFs which can be incorporated into macroscale and porous supports for convenient applications. Herein, the present study proposes to develop a composite material which combines advantageous features of macroscale/porous supports, and nanoscale functionality of MOFs. In particular, copper foam (CF) is selected as a macroscale porous medium, which is covered by nanoflower-structured CoO to increase surfaces for growing a cobaltic MOF, ZIF-67. The resultant composite comprises of CF covered by CoO nanoflowers decorated with ZIF-67 to form a hierarchical 3D-structured catalyst, enabling this ZIF-67@Cu foam (ZIF@CF) a promising catalyst for reducing 4-NP, and other NCCs. Thus, ZIF@CF can readily reduce 4-NP to 4-AP with a significantly lower Ea of 20 kJ/mol than reported values. ZIF@CF could be reused over 10 cycles and remain highly effective for 4-NP reduction. ZIF@CF also efficiently reduces other NCCs, such as 2-nitrophenol, 3-nitrophenol, methylene blue, and methyl orange. ZIF@CF can be adopted as catalytic filters to enable filtration-type reduction of NCCs by passing NCC solutions through ZIF@CF to promptly and conveniently reduce NCCs. The versatile and advantageous catalytic activity of ZIF@CF validates that ZIF@CF is a promising and practical heterogeneous catalyst for reductive treatments of NCCs.

Influence of Phosphorus Doping on Triazole-Based g-C3N5 Nanosheets for Enhanced Photoelectrochemical and Photocatalytic Performance.

Triazole-based g-C3N5, a potential catalyst, has received little attention over the years. We prepared phosphorus-doped g-C3N5 with one triazole and two triazine units for the first time to investigate its photoelectrochemical (PEC) and photocatalytic properties. The doping states and crystalline structures of the samples were determined using X-ray techniques, namely, X-ray diffraction, X-ray photoelectron spectroscopy, and X-ray absorption fine structure analysis. Our results suggested that the phosphorus was substituted into carbon sites form P-N/P═N bonds with four coordination, which contribute P 2p level donor states in the band gap to enhance light absorption and reduce charge separation. Therefore, P-doped g-C3N5 exhibited higher PEC current density and better photocatalytic efficiency toward the degradation of rhodamine B dye or tetracycline under light irradiation compared to the undoped g-C3N5 sample. However, excess phosphorus doping resulted in the formation of impurities and disrupted the triazine and triazole units, reducing the PEC and photocatalytic efficiency. In summary, P-doped g-C3N5 was successfully prepared in the present study and represents a promising, facile, and effective catalyst for energy applications and environmental remediation.

Photoluminescence quenching of thermally treated waste-derived carbon dots for selective metal ion sensing.

In the present study, carbon-dots (CDs) were derived from the thermal oxidation of an agricultural waste, bitter tea residue, to obtain different sp2/sp3 ratios and electronic structures for metal sensing. The CDs obtained from calcination at 700 °C exhibited the highest photoluminescence (PL) quantum yield (QY) of 11.8% among all the samples treated at different temperatures. These CDs had a high degree of graphitization, which resulted in a strong π-π* electron transition, and hence in a high QY. The strong photoluminescence of the CDs could be used to sense the metal ions Ag+, Sr2+, Fe2+, Fe3+, Co2+, Ni2+, Cu2+, and Sn2+ by monitoring their PL intensity at an excitation wavelength of 320 nm. The metals inhibited the PL intensity in the order Ag+ > Fe2+, Fe3+, Ni2+ > Sr2+, Co2+, Cu2+, Sn2+, which demonstrated that the CDs exhibited high metal ion detection capability and selectivity. The detection of Fe3+ using CDs was performed in the range of 10-100 ppm with a LOD (limit of detection) value of 0.380 ppm. Theoretical calculations demonstrated that Ag+, Sr2+, and Sn2+ induced charge transfer excitation and that Fe2+ and Ni2+ induced d-d transitions via complexation with the sp2 clusters. The charge transfer excitation and d-d transitions hindered the π-π* transition of the sp2 clusters, leading to a quenching effect. On the other hand, Li+, Na+, and K+ ions did not alter the π-π* transition of the sp2 clusters, resulting in a negligible quenching effect. In summary, the oxidation level and electronic structure of CDs derived from bitter tea residue could be tailored, and the CDs were shown to be a facile, sustainable, and eco-friendly material for metal sensing.

Cobalt ferrite nanoparticle-loaded nitrogen-doped carbon sponge as a magnetic 3D heterogeneous catalyst for monopersulfate-based oxidation of salicylic acid.

As salicylic acid (SAL) is increasingly consumed as a pharmaceutical product, release of SAL into the environment poses threats to ecology because of its low bio-degradability. Thus, SO4•--based chemical oxidation processes have been proposed for degrading SAL. Since monopersulfate (MPS) represents a primary reagent for generating SO4•-, and Co is the most capable metal for activating MPS to generate SO4•-, C3O4 NPs are frequently proposed for activating MPS but they are difficult to recover from water. Thus CoFe2O4 is considered as a magnetic alternative to Co3O4, and loading of CoFe2O4 NPs on substrates could further improve dispersion and avoid aggregation of NPs. Therefore, this study proposes a 3-Dimensional (3D) hierarchical catalyst which is fabricated by loading CoFe2O4 NPs on nitrogen-doped carbon sponge (NCS). The NCS is not only adopted as a support for CoFe2O4 NPs but also provides additional catalytic sites and enhances catalytic activities of CoFe2O4 NPs for MPS activation. As a result, CoFe2O4 NPs loaded on NCS (CFNCS) exhibits substantially higher catalytic activities than CoFe2O4 NPs and NCS individually with 100% of SAL could be afforded within 30 min. Ea of SAL degradation of 47.4 kJ/mol by CFNCS-activated MPS is also lower than those by other reported catalysts, whereas the RSE was 11.1%, which was also much higher than most of reported values. These features demonstrate that CFNCS is a promising 3D catalyst for enhancing MPS activation to degrade SAL. The findings obtained here are also insightful to develop efficient MPS-activating catalysts for eliminating contaminants.

De Novo synthesis of platinum-nanoparticle-encapsulated UiO-66-NH2 for photocatalytic thin film fabrication with enhanced performance of phenol degradation.

The structural and chemical stability of UiO-66-NH2 and its simulated solar irradiation responsive characteristic make it a suitable metal-organic framework (MOF) candidate as photocatalytic material. Platinum nanoparticles (Pt NPs) are typically immobilized in MOF to enhance the photocatalytic efficiency. However, introducing high metal content in MOF with high dispersion is still challenging using conventional methods. In this paper, we present de novo synthesis of Pt@UiO-66-NH2, which can reach a highest metal content of 16 wt% with an average nanoparticle size of around 2 nm as confirmed by ICP-MS analysis and TEM images. The presence of benzoic acid plays multiple important roles in Pt@UiO-66-NH2 formation, including binding formation with Zr clusters, facilitating Pt dispersion, and being a modulator in MOF construction. In addition, the Pt@UiO-66-NH2 is fabricated on the α-Al2O3 substrate as a photocatalytic membrane reactor (PMR) for phenol degradation, which shows over 70 % removal efficiency under light irradiation and H2O2 addition. The recycle test shows that the PMR can maintain high catalytic efficiency. The facile de novo synthesis method proposed in this study enables effective immobilization of high metal content in MOF, and construction of membrane-based photocatalyst for scale-up application.

Development of 3-dimensional Co3O4 catalysts with various morphologies for activation of Oxone to degrade 5-sulfosalicylic acid in water.

Since 5-sulfosalicylic acid (SFA) has been increasingly released to the environment, SO4--based oxidation processes using Oxone have been considered as useful methods to eliminate SFA. As Co3O4 has been a promising material for OX activation, the four 3D Co3O4 catalysts with distinct morphologies, including Co3O4-C (with cubes), Co3O4-P (with plates), Co3O4-N (with needles) and Co3O4-F (with floral structures), are fabricated for activating OX to degrade SFA. In particular, Co3O4-F not only exhibits the highest surface area but also possesses the abundant Co2+ and more reactive surface, making Co3O4-F the most advantageous 3D Co3O4 catalyst for OX activation to degrade SFA. The mechanism of SFA by this 3D Co3O4/OX is also investigated and the corresponding SFA degradation pathway has been elucidated. The catalytic activities of Co3O4 catalysts can be correlated to physical and chemical properties which were associated with particular morphologies to provide insights into design of 3D Co3O4-based catalysts for OX-based technology to degrade emerging contaminants, such as SFA.

Influence of Photocatalysis on Blood Cell Attachment over Protein-Immobilized Polystyrene Surfaces Modified with a Poly(styrene)-b-Poly(acrylic acid) Copolymer.

In the present study, thrombocytes, erythrocytes, and leukocytes were individually brought into contact with different immobilized blood proteins on the surface of polystyrene (PS), which was modified with a poly(styrene)-b-poly(acrylic acid) copolymer. When the concentration of fibronectin was greater than 5 µg mL-1, the attachment of erythrocytes increased, which indicated that the modified PS surface was less compatible with erythrocytes. In addition, vitronectin and laminin attached on the surface increased the adhesion of thrombocytes; higher adhesion was observed for leukocytes in the cases of fibrinogen, lysozyme, and laminin. Interestingly, adhesion properties of blood cells on the protein surface could be influenced by the addition of metal oxide- and carbon-based photocatalysts. After a photocatalytic treatment by metal oxide-based TiO2, the adhesion amounts of erythrocytes improved slightly, whereas the adhesion of leukocytes and thrombocytes decreased after treatment with a carbon-based g-C3N4 nanosheet. Our results suggested that the surface modification of the substrate through photocatalysis using various photocatalysts along with the grafting of the poly(styrene)-b-poly(acrylic acid) copolymer could be a promising approach to alternatively control the blood compatibility on the protein surface.

Novel Architecture Titanium Carbide (Ti3C2Tx) MXene Cocatalysts toward Photocatalytic Hydrogen Production: A Mini-Review.

Low dimensional transition metal carbide and nitride (MXenes) have been emerging as frontier materials for energy storage and conversion. Ti3C2Tx was the first MXenes that discovered and soon become the most widely investigated among the MXenes family. Interestingly, Ti3C2Tx exhibits ultrahigh catalytic activity towards the hydrogen evolution reaction. In addition, Ti3C2Tx is electronically conductive, and its optical bandgap is tunable in the visible region, making it become one of the most promising candidates for the photocatalytic hydrogen evolution reaction (HER). In this review, we provide comprehensive strategies for the utilization of Ti3C2Tx as a catalyst for improving solar-driven HER, including surface functional groups engineering, structural modification, and cocatalyst coupling. In addition, the reaming obstacle for using these materials in a practical system is evaluated. Finally, the direction for the future development of these materials featuring high photocatalytic activity toward HER is discussed.

Sulfur-doped g-C3N4 nanosheets for photocatalysis: Z-scheme water splitting and decreased biofouling.

In this study, an S-doped g-C3N4 nanosheet was prepared as a photocatalyst for effective oxygen evolution reaction. Sulfur plays a crucial role in S-doped g-C3N4 not only in increasing the charge density but also in reducing the energy band gap of S-doped g-C3N4 via substitution of nitrogen sites. S-doped g-C3N4 can serve as an oxygen-evolved photocatalyst, when combined with Ru/SrTiO3:Rh in the presence of [Co(bpy)3]3+/2+ as an electron mediator, enables photocatalytic overall water splitting under visible light irradiation with hydrogen and oxygen production rates of 24.6 and 14.5 µmol-h-1, respectively. Moreover, the photocatalytic overall water splitting to produce H2 and O2 using this Z-scheme system could use for five runs to at least 94.5 h under visible light irradiation. On the other hand, S-doped g-C3N4 can reduce biofouling by bacteria such as Escherichia coli by more than 70%, by simply incubating the S-doped g-C3N4 sample with bacterial solution under light irradiation. Our results suggest that S-doped g-C3N4 is a potentially effective, green, and promising material for a variety of photocatalytic applications.

Synergistic Effect of Hydrochloric Acid and Phytic Acid Doping on Polyaniline-Coupled g-C3N4 Nanosheets for Photocatalytic Cr(VI) Reduction and Dye Degradation.

In this study, graphitic carbon nitride (g-C3N4) nanosheets (CNns) were modified using polyaniline (PANI) codoped with an inorganic (hydrochloric acid, HCl) and an organic (phytic acid, PA) acid. Our results revealed that these samples exhibited extended visible-light absorption and a three-dimensional (3D) hierarchical structure with a large specific surface area. They also inhibited photoluminescence emission, reduced electrical resistance, and provided abundant free radicals, resulting in high photocatalytic performance. The PANI/g-C3N4 sample demonstrated outstanding photocatalytic activity of a Cr(VI) removal capacity of 4.76 mg·min-1·gc-1, which is the best record for the reduction of a 100 ppm K2Cr2O7 solution. Moreover, g-C3N4 coupled with PANI monotonically doped with HCl or PA did not demonstrate increased activity, suggesting that the codoping of HCl and PA plays a significant role in enhancing the performance. The improved photocatalytic activity of PANI/g-C3N4 can be attributed to the interchain and intrachain doping of PA and HCl over PANI, respectively, to create a 3D connected network and synergistically increase the electrical conductivity. Therefore, new insights into g-C3N4 coupled with PANI and codoped by HCl and PA may have excellent potential for the design of g-C3N4-based compounds for efficient photocatalytic reactions.

Amine functionalized ZIF-8 as a visible-light-driven photocatalyst for Cr(VI) reduction.

Hexavalent chromium (Cr(VI)) is one of the most toxic and carcinogenic species known to living beings, the environment, and our eco-system. Thus, it is urgent to develop a facile and effective approach for Cr(VI) removal. Zinc-based zeolitic imidazolate frameworks (ZIF-8), a typical metal organic framework, have high porosity, large specific surface area, high chemical stability, and abundant surface grafting sites. These sites can be easily modified with ethylenediamine (EDA) using a solvothermal process to generate a material that can serve as a potential candidate for photocatalytic Cr(VI) reduction under visible light irradiation. Various EDA contents and synthetic conditions were adopted in an attempt to investigate the correlation between ZIF-8 amine-functionalization and photocatalytic Cr(VI) reduction. The amine functionalization and the grafting sites on ZIF-8 were determined to be located at the -CH3 site of the 2-methylimidazole chains via X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), and nuclear magnetic resonance spectroscopy (NMR). Under optimum conditions, amine-functionalized ZIF-8 exhibited a normalized rate constant (k/specific surface area, kSSA), which was 9.8 times higher than that of unmodified ZIF-8 one for photocatalytic Cr(VI) reduction. The increased catalytic activity and range of visible light absorption of amine-functionalized ZIF-8 can be attributed to the increase in electron density due to the lone pairs of the surface grafted amines. In summary, amine-functionalized ZIF-8 could serve as a promising visible-light-active photocatalyst for environmental remediation.

Photocatalytic Dye and Cr(VI) Degradation Using a Metal-Free Polymeric g-C3N4 Synthesized from Solvent-Treated Urea.

The development of visible-light-driven polymeric g-C3N4 is in response to an emerging demand for the photocatalytic dye degradation and reduction of hexavalent chromium ions. We report the synthesis of g-C3N4 from urea treated with various solvents such as methanol, ethanol, and ethylene glycol. The samples were characterized and the Williamson⁻Hall method was applied to investigate the lattice strain of the samples. The activity of the samples was evaluated by observing the degradation of methyl orange and K2Cr2O7 solution under light irradiation. Photocatalytic reaction kinetics were determined as pseudo-first-order and zero-order for the degradation of methyl orange and reduction of hexavalent chromium, respectively. Due to the inhibited charge separation resulting from the small lattice strain, reduced crystal imperfection, and sheet-like structure, g-C3N4 obtained from ethanol-treated urea exhibited the highest activity among the evaluated samples.