Visible Light Absorption Range Research Articles

Huge redshift of absorption edge in a novel Z-type Bi2Sn2O7/α-Bi2O3 junction for highly efficiently visible light degradation of norfloxacin and bisphenol AF

Heterojunction was mainly used to realize the separation of charge carrier in current studies, but it did not bring about any other effect. In this paper, Bi2Sn2O7 was introduced into α-Bi2O3 to construct a direct Z-type Bi2Sn2O7/α-Bi2O3 heterojunction. It not only accelerated the rapid separation of electrons and holes, but also induced a huge redshift of absorption edge to enlarge the visible light absorption range. Such result led into the optimal sample being able to degrade 95% of norfloxacin and 92% of bisphenol AF for 90min of visible light irradiation. Under the same testing conditions, the removal efficiency of these two pollutants in the drinking water also attained 94% and 90% to demonstrate a good application. Moreover, the cycling test results indicated that the Bi2Sn2O7/α-Bi2O3 could be sustainably utilized. The electrons, holes, superoxide radical (•O2-) and hydroxyl radical (•OH) were the active substances in the process of degradation. The numbers of the Escherichia coli were 0.69×106 CFU/mL and 0.75×106 CFU/mL in the solutions after degradation to denote non-toxicity of the final products. Thus the Bi2Sn2O7/α-Bi2O3 composite could be applied in purification of various waste waters.

Interlayer Potassium Single-Atom-Coordinated g-C3N4 for Significantly Boosted Visible Light Photocatalytic H2 Production.

In recent years, graphitic carbon nitride (g-C3N4) has attracted considerable attention because it includes earth-abundant carbon and nitrogen elements and exhibits good chemical and thermal stability owing to the strong covalent interaction in its conjugated layer structure. However, bulk g-C3N4 has some disadvantages of low specific surface area, poor light absorption, rapid recombination of photogenerated charge carriers, and insufficient active sites, which hinder its practical applications. In this study, we design and synthesize potassium single-atom (K SAs)-doped g-C3N4 porous nanosheets (CM-KX, where X represents the mass of KHP added) via supramolecular self-assembling and chemical cross-linking copolymerization strategies. The results show that the utilization of supramolecules as precursors can produce g-C3N4 nanosheets with reduced thickness, increased surface area, and abundant mesopores. In addition, the intercalation of K atoms within the g-C3N4 nitrogen pots through the formation of K-N bonds results in the reduction of the band gap and expansion of the visible-light absorption range. The optimized K-doped CM-K12 nanosheets achieve a specific surface area of 127 m2 g-1, which is 11.4 times larger than that of the pristine g-C3N4 nanosheets. Furthermore, the optimal CM-K12 sample exhibits the maximum H2 production rate of 127.78 μmol h-1 under visible light (λ ≥ 420 nm), which is nearly 23 times higher than that of bare g-C3N4. This significant improvement of photocatalytic activity is attributed to the synergistic effects of the mesoporous structure and K SAs doping, which effectively increase the specific surface area, improve the visible-light absorption capacity, and facilitate the separation and transfer of photogenerated electron-hole pairs. Besides, the optimal sample shows good chemical stability for 20 h in the recycling experiments. Density functional theory calculations confirm that the introduction of K SAs significantly boosts the adsorption energy for water and decreases the activation energy barrier for the reduction of water to hydrogen.

All-organic heterojunctions used for the excellent photocatalytic H2O2 synthesis: The key role of bay-position Cl in PDI

Melem is the basic structural unit of g-C3N4. When directly utilized as a photocatalyst, the separation efficiency of photogenerated electron-hole pairs is low. In this study, we constructed a Melem-based all-organic heterojunction (PICN) by reacting the -NH2 at the terminal of the Melem unit with the anhydride of PDA. The photocatalytic efficiency for H2O2 production of the heterojunction is 4.2 times that of CN. Introducing -Cl at the bay position of PDI further enhances the photocatalytic H2O2 production efficiency by 1.6 times. This enhancement is attributed to the introduction of -Cl, which not only broadens the UV–visible light absorption range of the sample but also improves the interface electron transfer efficiency between Melem and PDICl. Moreover, the introduction of -Cl can also reduce the overpotential of the O2 reduction reaction on the surface of the sample. These novel findings may provide insights for the design of organic heterojunction photocatalysts.

Enhanced photocatalytic activities of FCNO nanoparticles on graphitic carbon nitride

Efficient charge separation and broadened light absorption are of crucial importance for photocatalytic environmental remediation, and graphitic carbon nitride (g-C3N4) is a very promising photocatalyst for this purpose. Herein, the synthesis of FCNO nanoparticles embedded within graphitic carbon nitride (g-C3N4) by hydrothermal route assisted with pyrolysis of urea was presented. The g-C3N4 was obtained from an abundantly available precursor urea and the synthesis process played double role. Urea reacted with metal salts to convert them into metallic oxides and yielded g-C3N4. The experimental results revealed the in-situ fabrication of FCNO nanoparticles and formation of g-C3N4. The band gap narrowing made it possible that the samples were able to show a wide range of visible light absorption which made them suitable for photocatalytic activity studies. Thus, the materials were utilized for the visible light-based photocatalytic degradation of methylene blue dye. Photocatalytic degradation efficiency with ~93 % was achieved by the composite FCNO/g-C3N4 (50:50). The present approach for the synthesis of materials was proved to be cost-effective and time saving which enabled their use as recyclable photocatalyst.

Facile fabrication of CeO2/L-Bi2O2CO3 composite photocatalyst for removal of ciprofloxacin under visible light irradiation

The application of semiconductor photocatalytic technology to degrade antibiotics in water has been proved to be a promising technology CeO2/L-Bi2O2CO3 composite photocatalyst was efficiently prepared by a facile room temperature precipitation technique and employed in the photocatalytic degradation of ciprofloxacin (CIP). When the concentration of ciprofloxacin was 20 mg/L and the dosage of catalyst was 1.0 g/L, the degradation rate of CIP was 89.96 % after 120 min reaction with optimal catalyst. The addition of L-cysteine not only changed the crystallinity of Bi2O2CO3, but also broadened its visible light absorption range. Additionally, the combination of CeO2 and L-Bi2O2CO3 creates a heterojunction interface accelerates the electron transfer, thereby improving the photocatalytic activity. The degradation process was confirmed to involve the significant participation of O2– and h+ through free radical capture experiments. HPLC-MS analysis detected the intermediates of CIP degradation, leading to the proposition of two potential degradation pathways. Moreover, an electron transfer mechanism was suggested by analyzing the Mott-Schottky (M−S) curve and Taut-plot curves. This work provides new paradigm for the rational design of modified Bi2O2CO3-based photocatalysts and the treatment of contain CIP wastewater.

Bifunctional Co3O4/g-C3N4 Hetrostructures for Photoelectrochemical Water Splitting.

This study explored the synergistic potential of photoelectrochemical water splitting through bifunctional Co3O4/g-C3N4 heterostructures. This novel approach merged solar panel technology with electrochemical cell technology, obviating the need for external voltage from batteries. Scanning electron microscopy and X-ray diffraction were utilized to confirm the surface morphology and crystal structure of fabricated nanocomposites; Co3O4, Co3O4/g-C3N4, and Co3O4/Cg-C3N4. The incorporation of carbon into g-C3N4 resulted in improved catalytic activity and charge transport properties during the visible light-driven hydrogen evolution reaction and oxygen evolution reaction. Optical properties were examined using UV-visible spectroscopy, revealing a maximum absorption edge at 650 nm corresponding to a band gap of 1.31 eV for Co3O4/Cg-C3N4 resulting in enhanced light absorption. Among the three fabricated electrodes, Co3O4/Cg-C3N4 exhibited a significantly lower overpotential of 30 mV and a minimum Tafel slope of 112 mV/dec This enhanced photoelectrochemical efficiency was found due to the established Z scheme heterojunction between Co3O4 and gC3N4. This heterojunction reduced the recombination of photogenerated electron-hole pairs and thus promoted charge separation by extending visible light absorption range chronoamperometric measurements confirmed the steady current flow over time under constant potential from the solar cell, and thus it provided the effective utilization of bifunctional Co3O4/g-C3N4 heterostructures for efficient solar-driven water splitting.

The construction of Z-scheme heterojunction ZnIn2S4@CuO with enhanced charge transfer capability and its mechanism study for the visible light degradation of tetracycline

In this study, copper oxide (CuO) was prepared by the microwave-assisted hydrothermal technique subsequently, CuO was grown in situ onto different rare metal compounds to prepare Z-scheme heterojunctions to improve the degradation efficiency of tetracycline (TC) in water environments. Various characterization proved the successful synthesis of all composite materials, and the formation of tight heterojunction interfaces, among which, the core–shell structure ZnIn2S4@CuO exhibited excellent photocatalytic degradation capability. Research results indicated that the degradation efficiency of ZnIn2S4@CuO for TC (50 mg/L) in the water environment reached 95.8 %, and the degradation rate is 2.41 times and 12.93 times that of CuO and ZnIn2S4 alone, respectively, the reason is because of the introduction of ZnIn2S4, Z-scheme heterojunction structures and internal electric field (IEF) is constructed and formed to extend the visible light response range of photocatalysts to improve electron-hole separation efficiency, and enhance charge transfer. In addition, ZnIn2S4@CuO-2 exhibited good stability and reproducibility, with no significant loss of activity after five cycles. Finally, the precise locations of free radical attack on TC were investigated by the combined use of high-resolution mass spectrometry (HR-MC) and frontier electron densities (FEDs), and a reasonable degradation pathway was provided. The results of this research provide a new and viable approach to overcome the limitations of conventional photocatalytic materials in terms of limited visible light absorption range and fast carrier recombination rates, which offers promising prospects for a wide range of applications in the field of wastewater purification.

Ultrafast photosensitized degradation of xanthates by using methylene blue as photosensitizer under simulated and natural solar light irradiation: Operational parameters, mechanism and toxicity evolution

Xanthates have attracted considerable attention due to their broad applications in mineral flotation process and unique natures including environmental persistence and toxicity. This study proposed an innovative approach for the efficient xanthates treatment from mineral processing wastewater. Methylene blue (MB) with good water solubility and strong light absorption in visible range was used as the photosensitizer to degrade potassium ethyl xanthate (PEX) under homogeneous conditions. MB, even at a very low concentration (0.5 mg/L), was found to rapidly remove PEX in only 10 min whether under simulated or natural solar light irradiation. Besides, the influences of various operational parameters, including photosensitizer dosage, PEX concentration, pH, light intensity, common ions, and water source on the photosensitized oxidation process was evaluated and analyzed. The possible degradation path of PEX was investigated depending on the intermediates detected by Liquid chromatography-mass spectrometry (LC-MS), and the photosensitized degradation mechanism was further speculated and validated by the radicals quenching experiments and electron paramagnetic resonance (EPR) spectroscopy. Furthermore, the toxicity of PEX was assessed against Bullfrog tadpole and Lemna minor, and it was found to be greatly reduced after treating with MB photosensitization. Overall, it is the first time that MB is proved to be an outstanding candidate for actual flotation wastewater treatment, providing a more efficient, economical and greener alternative to conventional methods.

Hierarchical LaTiO2N/Sn3O4 heterojunction with intimate interface contact for enhanced photocatalytic water splitting

LaTiO2N/Sn3O4 heterojunction with type-II band structure and hierarchical microstructure was constructed by decorating Sn3O4 nanoflowers and nanoflakes intimately on the surface of LaTiO2N nanosheets via a facile hydrothermal method. Compared with pure Sn3O4 and bare LaTiO2N, the photocatalytic H2 evolution activity for LaTiO2N/Sn3O4 heterostructure was boosted by ∼3 and ∼52 times, respectively, reaching 887 μmol·h−1·gcat−1. The mechanism for the elevated photocatalytic performance was systematically disclosed on the basis of comprehensive characterizations. Specifically, the introduced LaTiO2N extended the visible light absorption range to ∼600 nm, endowing Sn3O4 with more photogenerated charge carriers. Subsequently, the type-II band structure expedited the separation and migration of charge carriers, diminishing the internal recombination, thereby enhancing the photocatalytic activity. This work affords a new avenue for designing tin oxide-based and oxynitrides-based heterojunction.

Highly efficient photoelectrochemical aptasensor based on CdS/CdTe QDs co-sensitized TiO2 nanoparticles designed for thrombin detection.

A photoelectrochemical (PEC) sensor for the sensitive detection of thrombin (TB) was established. Co-sensitized combination of TiO2 nanoparticles combined with modified cadmium sulfide and cadmium telluride quantum dots (CdS/CdTe QDs) was utilized as a photoactive material. Successful growth of CdS/CdTe quantum dots on mesoporous TiO2 films occuredby successive ion-layer adsorption and reaction. This interesting formation of co-sensitive structure is conducive to enhancing the photocurrent response by improving the use rate of light energy. Additionally, the step-level structure of CdS/CdTe QDs and TiO2 NPs shows a wide range of visible light absorption, facilitating the dissociation of excitons into free electrons and holes. Consequently, the photoelectric response of the PEC analysis platform is significantly enhanced. This constructed PEC aptasensor shows good detection of thrombin with a low detection limit (0.033pM) and a widelinear range (0.0001-100nM) in diluted actual human serum samples. In addition, this PEC aptasensor also has the characteristics of good stability and good reproducibility, which provides a novel insight for the quantitative measurement of other similar analytes.

Innovative syntheses of immobilized CuxO semiconductors grown on 3D prints and their photoelectrochemical activity for sulfamethoxazole degradation

Traditional copper oxide manufacturing processes require high energy consumption, high synthesis temperatures, and long process times. This study proposes an innovative additive manufacturing process to support immobilized copper oxide, offering greater design flexibility and customization. CuxO semiconductors were synthesized on 3D-printed substrates via the anodization process and evaluated for their effectiveness in degrading sulfamethoxazole (SMX). XRD analysis of the samples revealed the presence of both CuO and Cu2O crystalline phases, this mixture of oxides helps to expand the absorption range of visible light. The immobilized CuxO semiconductors exhibited band gaps ranging between 1.6 and 1.8 eV. Negative current densities and Mott-Schottky analysis confirmed the nature of the p-type semiconductor. Semiconductors grown by 3D printing demonstrated remarkable degradation capacity for the antibiotic sulfamethoxazole (SMX), achieving 60% degradation after 360 minutes under visible light. Kinetic degradation tends to be a first-order and zero-order model. TOC analysis further revealed the formation of reaction intermediates during SMX degradation, ultimately leading to the mineralization of the contaminant. Based on these results, we report, for the first time CuxO semiconductors grown on large 3D-printed substrates as promising photocatalysts for the degradation of emerging water pollutants. Based on these results, we report, for the first time, that CuxO semiconductors grown on large 3D-printed substrates are promising photocatalysts for the degradation of emerging water contaminants. Furthermore, it should be emphasized that the proposed method is faster and does not require subsequent thermal treatments for its functionalization, making it attractive for various industrial applications.

Photoelectrochemical sensor based on Sn3O4/CdS heterojunction for detecting glucose in the body and Cu(Ⅱ) ion

In this work, photoactive composites of Sn3O4/CdS at different ratios were synthesized by a solvothermal method. First, Sn3O4 was synthesized. To further improve its photoelectric performance, Sn3O4/CdS-X(X = n(Sn3O4)/n(CdS)) with different molar ratios were synthesized by solvothermal method. The composition, surface structure, valence state and optical properties of Sn3O4/CdS-X were studied by a series of characterization methods. The test results show that Sn3O4/CdS-X have better photoelectric performance than Sn3O4 and CdS. UV–visible diffuse reflectance spectroscopy (UV–vis DRS) and photoluminescence (PL) demonstrate Sn3O4/CdS-0.55 exhibits the broadest visible light absorption range (360 ∼ 540 nm) and the strongest ability of photogenerated carrier separation. Based on the above performance advantages, Sn3O4/CdS-0.55 was opted to construct the PEC sensor for glucose and Cu(Ⅱ) ion. The linear range for detecting glucose is 0.5 µM-40 mM, and the LOD is 0.067 µM (S/N = 3). For Cu(Ⅱ) ion, these values are 1–290 µM and 0.066 µM, respectively. Moreover, the sensor shows superior selectivity, stability, and reproducibility, which can be used to detect actual samples.

Silver sulfide anchored bismuth molybdate p-n heterojunction nano-coating with excellent photo-thermal self-healing performance

In this research, a self-healing nano-coating with excellent photo-thermal response to near-infrared (NIR) laser is prepared. This coating incorporates silver sulfide anchored bismuth molybdate (Ag2S@Bi2MoO6) into a shape memory epoxy resin to achieve for a good photo-thermal conversion capability. The Ag2S@Bi2MoO6 p-n heterojunction could photo-generate more electron-holes pairs under the NIR laser irradiation. Also, it shows a wider absorption range of visible light, leading to effectively absorb the light energy, generate enough heat to induce the shape memory recovery in the coating, and seal the scratch. The results indicate that the temperature of EP-1 % Ag2S@Bi2MoO6 coating has reached about 88 °C, while good self-healing and anti-corrosion properties with a self-healing rate of 88.41 % have been achieved. Furthermore, calculations based on Density Functional Theory and Finite Element Method pointed out that the formation of p-n heterojunction effectively has enhanced the photo-thermal effect. This research opens a new way for developing self-healing coatings with an ultra-fast response time and high self-healing efficiency.

Ulva lactuca L. extract bio-templated fabrication of CuO/ZnFe2O4 nanocomposites for photodegradation organic dye pollutants and in vitro biological activities

In this present work, a novel CuO/ZnFe2O4 nanocomposites has been fabricated via hydrothermal-assisted synthesis using Ulva lactuca L. extract as both a reducing and capping agent A comprehensive investigation such as structural, morphological, optical, and electronic properties of the CuO/ZnFe2O4 NCs were investigated in details. The photocatalytic efficacy of the prepared CuO/ZnFe2O4 NCs was assessed for Congo red (CR) dye degradation and the experimental results demonstrate the CuO/ZnFe2O4 NCs exhibits superior photocatalytic activity (91.13% k=0.03289 min−1) compared to pure CuO and ZnFe2O4 catalysts under 120 min of visible light irradiation. Additionally, the CuO/ZnFe2O4 NCs exhibited excellent long-term recycling stability over four consecutive cycles. This enhanced photocatalytic performance of CuO/ZnFe2O4 NCs was attributed to the synergism between CuO and ZnFe2O4, which facilitate the exceptional properties such as large specific area, a wide visible-light absorption range, and efficient electron-hole separation. Furthermore, the prepared CuO/ZnFe2O4 NCs were evaluated for their in vitro antibacterial and anticancer properties. The results of the disc diffusion assay with CuO/ZnFe2O4 NCs as an antibacterial agent demonstrated a highest zone of inhibition of 18.23 ± 0.30 mm for Bacillus subtilis and 19.83 ± 0.76 mm Escherichia coli. Moreover, in vitro cytotoxicity assessments using the MTT assay indicated a 64.94% cytotoxic activity against HT-29 colon cancer cells. The multifunctional advantages of Ulva lactuca L. extract-mediated green CuO/ZnFe2O4 NCs hold significant promise for environmental remediation and in vitro-based therapeutic applications.

Preparation of Z-type Cu2SnS3/g-C3N4 heterojunction material and its synergistic photocatalytic performance with H2O2

Due to poor visible light responsiveness and easy recombination of photo generated carriers, the photocatalytic performance of a single g-C3N4 is limited. This article presents a Z-type Cu2SnS3/g-C3N4 (CTS/CN) heterojunction photocatalyst prepared by in-situ growth of CTS on the surface of g-C3N4 using a simple solvothermal method. Through SEM results, it can be seen that as the content of g-C3N4 increases, the nanosheet gaps of flower shaped microspheres on the surface of CTS/CN increase and the size becomes thinner. The UV–vis DRS experiment showed that the introduction of CTS increased the visible light absorption range of CTS/CN composite and improved its visible light absorption ability.Under the synergistic effect of H2O2, the photocatalytic degradation efficiency of CTS/70% CN towards MO reached 99% at 50 minutes，At the same time, the degradation rate constants k of methylene blue (MB), ciprofloxacin (CIP) and levofloxacin (LEV) reached 0.06289 min−1, 0.02132 min−1 and 0.02787 min−1 respectively at 100 min.In the synergistic MO system of H2O2 for photocatalytic degradation, free radical capture experiments showed that the main active species were h+and • OH. Combined with the band structure of Cu2SnS3 and g-C3N4, a Z-type photocatalytic mechanism was proposed. Under visible light, H2O2 rapidly captured the photo generated electrons of CTS/CN, promoting the transport of photo generated carriers. This study provides theoretical guidance for the design and construction of Z-type heterojunctions with superior visible light driven photocatalytic performance.

Photostability and visible-light-driven photoactivity enhancement of hierarchical C@ZnCdS/ZnS/MoS2

Zinc cadmium sulfide solid (Zn x Cd1−x S) related composites received great attention in photocatalytic hydrogen production because of their tunable bandgap and strong visible light absorption range. But sulfide-based metal materials commonly suffer from photo-corrosion issues. It is very important to construct the photocatalysts with high efficient activity and photostability for H2 production. Herein, we successively prepared ZnCdS/ZnS (ZCS/ZS) heterostructures, ZnCdS/ZnS/MoS2 (ZCS/ZS/M) heterostructures decorated ZCS/ZS with MoS2 quantum dots, then we obtained x-C@ZCS/ZS and x-C@ZCS/ZS/M heterostructures encapsulated ZCS/ZS and ZCS/ZS/M with carbon layer. The performance of the photocatalytic hydrogen production showed that sample 0.05-C@ZCS/ZS/M has a remarkable photocatalytic H2 evolution rate of 15.231 mmol·h−1·g−1 with noble metal-free co-catalysts. This rate was approximately 21 times higher than that of the pristine ZCS/ZS photocatalyst. The optimized sample reveals an excellent stability, without activity losses after 10 h. The improved photocatalytic activity can be attributed to the unique heterojunction structure formed by ZCS/ZS and MoS2. Additionally, the carbon films played a crucial role in providing excellent stability by spatially separating the sites for redox reactions, thereby inhibiting the recombination of photo-generated electron–hole pairs.

12 Connecting Sites Linked Three‐dimensional Covalent Organic Frameworks with Intrinsic Non‐interpenetrated shp Topology for Photocatalytic H2O2 Synthesis

AbstractDeveloping high connectivity (>8) three‐dimensional (3D) covalent organic frameworks (COFs) towards new topologies and functions remains a great challenge owing to the difficulty in getting high connectivity organic building blocks. This however represents the most important step towards promoting the diversity of COFs due to the still limited dynamic covalent bonds available for constructing COFs at this stage. Herein, highly connected phthalocyanine‐based (Pc‐based) 3D COFs MPc‐THHI‐COFs (M=H2, Ni) were afforded from the reaction between 2,3,9,10,16,17,23,24‐octacarboxyphthalocyanine M(TAPc) (M=H2, Ni) and 5,5′,5′′,5′′′,5′′′′,5′′′′′‐(triphenylene‐2,3,6,7,10,11‐hexayl)hexa(isophthalohydrazide) (THHI) with 12 connecting sites. Powder X‐ray diffraction analysis together with theoretical simulations and transmission electron microscopy reveals their crystalline nature with an unprecedented non‐interpenetrated shp topology. Experimental and theoretical investigations disclose the broadened visible light absorption range and narrow optical band gap of MPc‐THHI‐COFs. This in combination with their 3D nanochannels endows them with efficient photocatalysis performance for H2O2 generation from O2 and H2O via 2e− oxygen reduction reaction and 2e− water oxidation reaction under visible‐light irradiation (λ >400 nm). This work provides valuable result for the development of high connectivity functional COFs towards diverse application potentials.

Efficient photocatalytic degradation of antibiotics by binary heterojunction complex boron subphthalocyanine bromide/bismuth oxychloride

The development of stable and efficient heterojunction photocatalysts for wastewater environmental purification exhibits a significant challenge. Herien, a promising binary heterojunction complex comprising boron subphthalocyanine bromide/bismuth oxychloride (SubPc-Br/BiOCl) was successfully synthesized using the hydrothermal method, which involved the self-assembled of SubPc-Br on the surface of BiOCl via intermolecular π-π stacking interactions to compose an electron-transporting layer. The photocatalytic efficiency of SubPc-Br/BiOCl for the degradation of tetracycline and the minocycline exhibited a substantial improvement of 29.14% and 53.72%, respectively, compared to the original BiOCl. Experimental characterization and theoretical calculations elucidated that the enhanced photocatalytic performance of the SubPc-Br/BiOCl composite photocatalysts stemmed from the S-scheme electron transport mechanism at the interface between BiOCl and SubPc-Br supramolecules, which broadened the visible light absorption range, increased the carrier molecular efficiency, and accelerated the carriers. Furthermore, molecular dynamic (MD) simulations provided insights into the action trajectories of the two semiconductors, revealing that the presence of SubPc-Br enhances the water and organic pollutant adsorption capabilities of the BiOCl surface within the supramolecular array system. In conclusion, the synthesis and analysis of the binary heterojunction complex SubPc-Br/BiOCl yield valuable insights into the efficient photocatalytic degradation of antibiotics, holding great promise for diverse environmental applications.

12 Connecting Sites Linked Three-dimensional Covalent Organic Frameworks with Intrinsic Non-interpenetrated shp Topology for Photocatalytic H2O2 Synthesis.

Developing high connectivity (>8) three-dimensional (3D) covalent organic frameworks (COFs) towards new topologies and functions remains a great challenge owing to the difficulty in getting high connectivity organic building blocks. This however represents the most important step towards promoting the diversity of COFs due to the still limited dynamic covalent bonds available for constructing COFs at this stage. Herein, highly connected phthalocyanine-based (Pc-based) 3D COFs MPc-THHI-COFs (M=H2, Ni) were afforded from the reaction between 2,3,9,10,16,17,23,24-octacarboxyphthalocyanine M(TAPc) (M=H2, Ni) and 5,5',5'',5''',5'''',5'''''-(triphenylene-2,3,6,7,10,11-hexayl)hexa(isophthalohydrazide) (THHI) with 12 connecting sites. Powder X-ray diffraction analysis together with theoretical simulations and transmission electron microscopy reveals their crystalline nature with an unprecedented non-interpenetrated shp topology. Experimental and theoretical investigations disclose the broadened visible light absorption range and narrow optical band gap of MPc-THHI-COFs. This in combination with their 3D nanochannels endows them with efficient photocatalysis performance for H2O2 generation from O2 and H2O via 2e- oxygen reduction reaction and 2e- water oxidation reaction under visible-light irradiation (λ >400 nm). This work provides valuable result for the development of high connectivity functional COFs towards diverse application potentials.

Performance Evaluation of a Multifunctional Road Marking Coating for Tunnels Based on Nano SiO2 and TiO2 Modifications

Multifunctional road marking coatings with the functions of high-temperature stability, degradation of exhaust gas, and self-cleaning are of great significance for the safe operation and environmental protection of tunnels. This article uses active acrylic resin and an organosilicon hydrophobic agent as the base material, selects expanded vermiculite and glass microspheres as insulation fillers, and uses ammonium polyphosphate, pentaerythritol, melamine, and aluminum hydroxide as high-thermal-stability systems to prepare a two-component road marking coating base material. Then, nano SiO2 and modified nano TiO2 are added as modifiers to prepare a multifunctional road marking coating for tunnels. The physical and chemical properties of multifunctional road marking coatings are evaluating based on laboratory tests including thermogravimetry and derivative thermogravimetry, differential scanning calorimetry, infrared spectroscopy, scanning electron microscopy, exhaust degradation, and contact angle tests. The results indicate that the developed multifunctional road marking coating effectively reduces the thermal conductivity of the carbon layer through physical changes in the flame retardant system and the heat resistance formed by the high breaking bond energy of nano SiO2 during the combustion process. It forms a ceramic-like structure of titanium pyrophosphate with nano TiO2 that is beneficial for improving flame retardancy without generating harmful volatile gases and has good flame retardant properties. N–V co-doping reduces the bandgap of TiO2, broadens the absorption range of visible light by nano TiO2, improves the catalytic efficiency of visible light, and achieves the degradation efficiency of the four harmful components NOx, HC, CO, and CO2 in automotive exhaust by 23.4%, 8.3%, 2.5%, and 2.9%, respectively. The solid–liquid phase separation in the multifunctional road marking coating in the tunnel causes the formation and accumulation of nano SiO2 and TiO2 particles on the coating surface, resulting in a microstructure similar to the “micro–nano micro-convex” on the lotus leaf surface and making a water droplet contact angle of 134.2° on the coating surface.