Amide Covalent Bonding Engineering in Heterojunction for Efficient Solar-Driven CO₂ Reduction

ACS Nano, Journal Year: 2023, Volume and Issue: 17(20), P. 20560 - 20569

Published: Oct. 4, 2023

Inefficient charge separation and slow interfacial reaction dynamics significantly hamper the efficiency of photocatalytic CO2 reduction. Herein, a facile EDC/NHS-assisted linking strategy was developed to enhance in heterojunction photocatalysts. Using this approach, we successfully synthesized amide-bonded carbon quantum dot-g-C3N4 (CQD-CN) The formation amide covalent bonds between CN CQDs CN-CQD facilitates efficient carrier migration, adsorption, activation. Exploiting these advantages, photocatalysts exhibit high selectivity with CO CH4 evolution rates 79.2 2.7 μmol g-1 h-1, respectively. These are about 1.7 3.6 times higher than those CN@CQD bulk CN, Importantly, demonstrate exceptional stability, even after 12 h continuous testing. presence COOH* signal is identified as crucial intermediate species conversion CO. This study presents bonding engineering for developing high-performance solar-driven reduction CO2.

Language: Английский

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Engineering Built‐In Electric Field Microenvironment of CQDs/g‐C₃N₄ Heterojunction for Efficient Photocatalytic CO₂ Reduction

Advanced Science, Journal Year: 2024, Volume and Issue: 11(28)

Published: May 10, 2024

Abstract Graphitic carbon nitride (CN), as a nonmetallic photocatalyst, has gained considerable attention for its cost‐effectiveness and environmentally friendly nature in catalyzing solar‐driven CO 2 conversion into valuable products. However, the photocatalytic efficiency of reduction with CN remains low, accompanied by challenges achieving desirable product selectivity. To address these limitations, two‐step hydrothermal‐calcination tandem synthesis strategy is presented, introducing quantum dots (CQDs) forming ultra‐thin CQD/CN nanosheets. The integration CQDs induces distinct work function CN, creating robust interface electric field after combination. This facilitates accumulation photoelectrons region, providing an abundant source reduced electrons process. Remarkably, nanosheets exhibit average yield 120 µmol g −1 , showcasing outstanding selectivity 92.8%. discovery not only presents innovative pathway development high‐performance photocatalysts grounded non‐metallic materials employing but also opens new avenues versatile application prospects environmental protection sustainable cleaning energy.

Language: Английский

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Materials Containing Single‐, Di‐, Tri‐, and Multi‐Metal Atoms Bonded to C, N, S, P, B, and O Species as Advanced Catalysts for Energy, Sensor, and Biomedical Applications

Advanced Science, Journal Year: 2024, Volume and Issue: 11(33)

Published: July 1, 2024

Abstract Modifying the coordination or local environments of single‐, di‐, tri‐, and multi‐metal atom (SMA/DMA/TMA/MMA)‐based materials is one best strategies for increasing catalytic activities, selectivity, long‐term durability these materials. Advanced sheet supported by metal atom‐based have become a critical topic in fields renewable energy conversion systems, storage devices, sensors, biomedicine owing to maximum utilization efficiency, precisely located centers, specific electron configurations, unique reactivity, precise chemical tunability. Several offer excellent support are attractive applications energy, medical research, such as oxygen reduction, production, hydrogen generation, fuel selective detection, enzymatic reactions. The strong metal–metal metal–carbon with metal–heteroatom (i.e., N, S, P, B, O) bonds stabilize optimize electronic structures atoms due interfacial interactions, yielding activities. These provide models understanding fundamental problems multistep This review summarizes substrate structure‐activity relationship different active sites based on experimental theoretical data. Additionally, new synthesis procedures, physicochemical characterizations, biomedical discussed. Finally, remaining challenges developing efficient SMA/DMA/TMA/MMA‐based presented.

Language: Английский

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Symmetrical Localized Built-in Electric Field by Induced Polarization Effect in Ionic Covalent Organic Frameworks for Selective Imaging and Killing Bacteria

ACS Nano, Journal Year: 2024, Volume and Issue: 18(5), P. 4539 - 4550

Published: Jan. 23, 2024

Photocatalytic materials are some of the most promising substitutes for antibiotics. However, antibacterial efficiency is still inhibited by rapid recombination photogenerated carriers. Herein, we design a cationic covalent organic framework (COF), which has symmetrical localized built-in electric field due to induced polarization effect caused electron-transfer reaction between Zn-porphyrin unit and guanidinium unit. Density functional theory calculations indicate that there electrophilic/nucleophilic region in COF structure, results from increased electron density around The formed local can further inhibit carriers driving transfer under light irradiation, greatly increases yield reactive oxygen species. This wrapped DSPE-PEG2000 selectively target lipoteichoic acid Gram-positive bacteria electrostatic interaction, be used selective discrimination imaging bacteria. Furthermore, this nanoparticle rapidly kill including 99.75% Staphylococcus aureus 99.77% Enterococcus faecalis at an abnormally low concentration (2.00 ppm) irradiation 20 min. work will provide insight into designing photoresponsive COFs through engineering charge behavior.

Language: Английский

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Multifunctional Roles of Ionic Microenvironments in the Preparation, Modification, and Application of g‐C₃N₄

Advanced Functional Materials, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 7, 2025

Abstract As a visible light‐responsive metal‐free polymer semiconductor, graphitic carbon nitride (g‐C 3 N 4 ) has garnered increasing attention in photocatalysis but needs structural modification and functional enhancement. Recently, the rational design of ionic microenvironments (IMEs) by leveraging tunability various ions to endow catalysts with tailored functionalities been elevated hot direction. To elucidate their respective effects on g‐C , IMEs are categorized into three types, namely plasma IMEs, organic inorganic according criteria external field dependence, cation type, application scenarios. These promotions include facilitated preparation, diversified modifications, improved efficiencies. First, participate constructing functionalized microenvironment through dynamic interactions precursor during facilitating customization, crystal nucleation growth, surface performance enhancement, process cleanliness. Second, create tunable for post‐modification functioning as an electron reservoir, modifier, substrate adsorbent, stabilizer. Lastly, synergistic effect between IME they achieve targeted product regulation, enhanced chemical stability, efficient adsorption, potential fields like catalysis, energy storage, gas adsorption. Also, limitations, challenges, prospects strategies discussed, offering systematic insights IMEs‐based structure‐activity relationships 4.

Language: Английский

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High Energy Density Aqueous Zinc–Chalcogen (S, Se, Te) Batteries: Recent Progress, Challenges, and Perspective

Advanced Energy Materials, Journal Year: 2023, Volume and Issue: 13(44)

Published: Oct. 11, 2023

Abstract Zinc‐ion batteries with chalcogen‐based (S, Se, Te) cathodes have emerged as a promising candidate for utility‐scale energy storage systems and portable electronics, which attracted rapid attention offer tremendous opportunities owing to their excellent density, on top of the advantages aqueous Zn including cost‐effectiveness, inherent safety, eco‐friendliness. Here, comprehensive overview basic mechanism zinc–chalcogen great intrinsic issues is provided. More detailed recent progress summarized existing challenges strategies are provided well. First, four specific types presented, including: zinc–sulfur, zinc–selenium, zinc–selenium sulfide, zinc–tellurium batteries. Second, remaining within in material preparation, physicochemical properties, battery performance discussed. Meanwhile, series constructive comprehensively put forward optimizing electrochemical performance. Finally, future research perspectives proposed exploration innovation next‐generation green zinc applications.

Language: Английский

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Modulating Triplet Excited States of Organic Semiconductors via Tuning Molecular Conformation for Dual‐ratiometric Thermometers

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(20)

Published: March 17, 2023

Abstract The dual‐ratiometric thermometry is one of highly accurate methods for microscopic thermal measurement in biological systems. Herein, a series chromone derivatives with noncovalently intramolecular interactions (NIIs) were designed and synthesized ratiometric thermometers. triplet states these organic compounds systematically tuned upon regulating the conformation NIIs to yield efficient room temperature phosphorescence large wavelength difference between fluorescence simultaneously. As result, an unprecedent 3D thermometer was established based on intensity ratio lifetime fluorescence/phosphorescence vs temperature, which used vitro vivo bio‐thermometry high accuracy. This work provides novel method achieve dual thermometers via tuning excited states.

Language: Английский

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Construction of a 1D/2D S-Scheme Heterojunction of Mo-Doped WO₃/In-Doped Carbon Nitride for Efficient Hydrogen Peroxide Photosynthesis

The Journal of Physical Chemistry C, Journal Year: 2024, Volume and Issue: 128(14), P. 5837 - 5847

Published: March 30, 2024

Polymeric carbon nitride (CN) is a promising photocatalyst in H2O2 photosynthesis due to its low cost and high 2e– oxygen reduction reaction (ORR) selectivity. However, the yield still unsatisfactory limited light absorption carrier recombination rate. Herein, an S-scheme heterojunction consisting of Mo-doped WO3 nanowires In-doped CN nanosheets (Mo-WO3/In-CN) was constructed. The exhibits remarkably enhanced photocatalytic performance with production rate 3082.9 μmol g–1 h–1, which 33.4 8.6 times those Mo-WO3 In-CN, respectively. Moreover, reaches 462.3 h–1 pure water. Mechanism studies demonstrate that produced through dual routes ORR water oxidation reaction. construction enhances visible improves separation efficiency redox ability photogenerated carriers. Meanwhile, increased surface area good hydrophilicity also contribute improved yield. This work provides insight into design high-efficiency photocatalysts for synthesis.

Language: Английский

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Constructing Single-Atom Active Sites Embedded in Hexagonal Boron Nitride for Adsorption and Sensing of Lithium Battery Thermal Runaway Gases

Langmuir, Journal Year: 2024, Volume and Issue: 40(19), P. 10334 - 10345

Published: May 1, 2024

The utilization and selectivity of single atoms have garnered significant attention among researchers. However, they are easy to agglomerate because their high surface energy. To overcome this challenge, it is crucial seek suitable carriers anchor metal achieve optimal performance. In work, the structures transition embedded in hexagonal boron nitride (MB2N2, M = Fe, Co, Ni, Cu, Zn) constructed used for adsorption sensing lithium battery thermal runaway gases (H2, CO, CO2, CH4) through DFT method. behavior MB2N2 was evaluated energy, sensitivity, recovery time. calculation results indicate that CoB2N2 exhibits strong capacity both H2 CO. sensitivity FeB2N2 toward CO as 3.232 × 1016. Subsequently, mechanism studied TDOS PDOS, showed hybridization between orbitals enhanced gas This study presents novel approaches designing single-atom developing sensors detecting gases.

Language: Английский

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Visual Eosin Y‐Based Photosensitization Sensing Systems for Ultrasensitive Detection of Diclofenac with Single‐Atom Co‐N₂O₂ site‐Immobilized g‐C₃N₄ Nanosheets

Advanced Materials, Journal Year: 2024, Volume and Issue: 36(31)

Published: June 5, 2024

Abstract It is highly desired to develop a visual sensing system for ultrasensitive detection of colorless diclofenac (DCF), yet with significant challenge. Herein, novel dye‐based photosensitization has been successfully developed detecting DCF the first time, in which used dye eosin Y (DeY) can strongly absorb visible light and then be decolorized obviously by transferring photogenerated electrons g‐C 3 N 4 nanosheets (CN), while built single‐atomic Co─N 2 O sites on CN boron‐oxygen connection competitively adsorb impede decoloration DeY. This exhibits broad range from 8 ng L −1 mg 535 nm light, an exceptionally low limit (3.5 ), remarkable selectivity. Through time‐resolved, situ technologies, theoretical calculations, decolorization DeY attributed disruption DeY's conjugated structure caused triplet excited state electron transfer CN, meanwhile, adsorbed oxygen facilitates charge process. The preferential adsorption mainly depends strong interactions between as‐constructed single‐atom Co Cl DCF. study opens innovative light‐driven combining metal/nanomaterial visually intuitive environmental pollutants.

Language: Английский

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