A Direct Z-Scheme Single-Atom MOC/COF Piezo-Photocatalytic System for Overall Water Splitting

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(14), P. 10447 - 10461

Published: June 26, 2024

Overall water splitting into H2 and H2O2 via Z-scheme piezo-photocatalytic systems is an ideal method for renewable energy production. Herein, we have synthesized a triangular prism-shaped metal–organic cage (MOC-Q3) integrating three catalytic Pd2+ centers two photosensitive ligands, which successfully immobilized on highly crystalline β-ketoenamine-linked covalent organic framework (EA-COF) to form single-atom photosystem. The optimized MOC-Q3/EA-COF achieves high yield (26.17 mmol g–1 h–1) with TONPd of 118,521 ascorbic acid as sacrificial agent due broad light absorption, effective carrier separation, widely distributed Pd active sites, among the highest COF-based solar evolution photocatalysts. Interestingly, EA-COF found be piezoelectric material its performance mainly in-plane polarization 2,4,6-trihydroxybenzene-1,3,5-tricarbaldehyde groups in COF, confirmed by experimental observations density functional theory calculations. shows production rates 239.94 400.38 μmol h–1, respectively, pure when excited ultrasound coupled irradiation. integration MOC-Q3 can further enhance efficiency splitting. superior exhibits generation 426.38 535.14 outperforming 1.8 1.3 times. This pioneering work construct MOC/COF system, provides efficient way use mechanical produce through overall

Language: Английский

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Cd Single Atom as an Electron Mediator in an S‐Scheme Heterojunction for Artificial Photosynthesis of H₂O₂

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

Published: Feb. 13, 2025

Abstract Developing conductor‐mediated S‐scheme heterojunction photocatalysts imitating natural photosynthetic systems emerges as a promising approach to hydrogen peroxide (H 2 O ) production. However, achieving precise coupling between two semiconductors with charge shuttle and modulating the interfacial interactions still remain significant bottleneck. Herein, we propose catalyst architecture Cd single atom mediated formed by interfacing CdS TiO nanoparticles. This exhibits an H production rate high 60.33 µmol g −1 min under UV–vis light irradiation, which is attributed efficient transport at interface of thanks S‐scheme. In‐situ X‐ray photoelectron spectroscopy (XPS) electron spin resonance (ESR) spin‐trapping tests confirm transfer route. Femtosecond transient absorption (fs‐TA) other ex‐situ characterizations further corroborate across interface. work offers new perspective on constructing atoms heterojunctions enhance photocatalytic performance.

Language: Английский

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Promoting Proton Donation through Hydrogen Bond Breaking on Carbon Nitride for Enhanced H₂O₂ Photosynthesis

ACS Nano, Journal Year: 2024, Volume and Issue: 18(31), P. 20435 - 20448

Published: July 26, 2024

Photocatalytic H2O2 production has attracted much attention as an alternative way to the industrial anthraquinone oxidation process but is limited by weak interaction between catalysts and reactants well inefficient proton transfer. Herein, we report on a hydrogen-bond-broken strategy in carbon nitride for enhancement of photosynthesis without any sacrificial agent. The promoted hydrogen bond formation exposed N atoms H2O molecules, which enhances proton-coupled electron transfer therefore photocatalytic activity. serve buffering sites from molecules nitride. also enhanced through adsorption reduction O2 gas toward because nitrogen vacancies (NVs) cyano groups after intralayer breaking A high light-to-chemical conversion efficiency (LCCE) value 3.85% achieved. are found undergo one-step two-electron pathway photogenerated hot electrons four-electron produce gas, respectively. Density functional theory (DFT) calculations validate reaction pathways. This study elucidates significance catalyst reactants, greatly increases tunneling dynamics.

Language: Английский

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Promoted Hydrogen Peroxide Production from Pure Water on g‐C₃N₄ with Nitrogen Defects Constructed through Solvent‐Precursor Interactions: Exploring a Complex Story in Piezo‐Photocatalysis

Small Methods, Journal Year: 2024, Volume and Issue: unknown

Published: July 31, 2024

Abstract Hydrogen peroxide (H 2 O ) production via oxygen (O reduction reaction (ORR) in pure water O) through graphitic carbon nitrides (g‐C 3 N 4 )‐based piezo‐photocatalysts is an exciting approach many current studies. However, the low Lewis‐acid properties of g‐C limited catalytic performance because adsorption efficacy. To overcome this challenge, interaction precursors with various solvents are utilized to synthesize , possessing multiple nitrogen‐vacant species thermal shocking polymerization. These results suggest that lack nitrogen and incident introduction oxygen‐functional groups enhance Lewis acid‐base interactions polarize lattices, leading enormous enhancement. Furthermore, mechanisms thoroughly studied, formation H proceeding radical oxidation pathways, which roles light ultrasound carefully investigated. Thus, these findings not only reinforce potential view metal‐free photocatalysts, accelerating understanding working principles generate based on reactions, but also propose a facile one‐step way for fabricating highly efficient scalable photocatalysts produce without using sacrificial agents, pushing practical application situ solar toward real‐world scenarios.

Language: Английский

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Unlocking the Origin of Enhanced Piezo‐Photocatalytic Performance via Thermodynamic Insights: A Study of Surface Active‐Site Engineering in ZnO

Small, Journal Year: 2025, Volume and Issue: unknown

Published: April 21, 2025

Abstract Engineering active sites to boost the catalytic performance of semiconducting materials is current interest. Herein, enhanced hydrogen peroxide (H 2 O ) production via oxygen (O reduction through a surface‐substituting strategy reported, in which surface Zn─O bonds are partially halogenated one‐step simple calcination process. The experimental data validated presence halogen on modulated band structures prepared materials, leading with optimal samples, ZnO‐Cl, generating up 6.3 µmol h −1 H under piezo‐photocatalytic conditions from pure water. In addition, theoretical calculation demonstrates binding energy for halogen‐defecting would be more stable adsorption than pristine ZnO. Furthermore, thermodynamic states piezo‐catalytic, piezocatalytic, and photocatalytic also evaluated temperature‐dependent aerobic degradation methylene blue (MB). results show that piezo‐photocatalysis can help enhance by lowering activation barrier, relate entropy‐enthalpy compensation effects. This study not only provides approach synthesizing highly catalysts produce but interprets fundamental insights into how ultrasound outcomes, benefiting both material communities.

Language: Английский

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Promoted Hydrogen Peroxide Production from Pure Water on g-C3N4 with Nitrogen Defects Constructed through Solvent-Precursor Interactions: Exploring A Complex Story in Piezo-Photocatalysis

Published: May 21, 2024

Hydrogen peroxide (H2O2) production via oxygen (O2) reduction reaction (ORR) in pure water (H2O) through graphitic carbon nitrides (g-C3N4)-based piezo-photocatalysts is an exciting approach many current studies. However, the low Lewis-acid properties of g-C3N4 limited catalytic performance because O2 adsorption efficacy. To overcome this challenge, we utilized interaction precursors with various solvents to synthesize g-C3N4, possessing multiple nitrogen-vacant species thermal shocking polymerization. Our results suggest that lack nitrogen and incident introduction oxygen-functional groups enhance Lewis acid-base interactions polarize lattices, leading enormous enhancement, roughly 7 times from optimal samples compared pristine piezo-photocatalysis. Meanwhile, also observed correlation between charge separation kinetic crystalline degree synthesized materials, which can elucidate how defects impacted outcomes. Furthermore, mechanisms were thoroughly studied, formation H2O2 proceeding radical oxidation pathways, roles light ultrasound carefully investigated. Thus, our findings not only reinforce potential view metal-free photocatalysts, accelerating understanding working principles generate based on reactions, but propose a facile one-step way for fabricating highly efficient scalable photocatalysts produce without using sacrificial agents, pushing practical application in-situ solar toward real-world scenarios.

Language: Английский

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Deciphering the impacts of symmetric and asymmetric structures in heptazine units over g-C3N4 on piezo-photocatalysis for H2O2 production from pure water

Chemical Engineering Journal, Journal Year: 2024, Volume and Issue: unknown, P. 158657 - 158657

Published: Dec. 1, 2024

Language: Английский

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Hybrid piezo-photocatalysts: Harnessing dual functionalities for advanced charge dynamics and catalytic performance

Chemical Engineering Journal, Journal Year: 2024, Volume and Issue: 500, P. 157440 - 157440

Published: Nov. 1, 2024

Language: Английский

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