Keto-enol tautomerism as transformative electron/hole traps to promote charge carrier separation for record-high H2O2 photosynthesis in real world DOI Creative Commons
Tianyi Ma, Fang Ma, Xiaodong Sun

et al.

Research Square (Research Square), Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 30, 2024

Abstract Covalent organic frameworks (COFs) are excellent photocatalysts for hydrogen peroxide (H2O2) photosynthesis, but often limited by retarded charge carrier separation. Presently, donor-acceptor (D-A) type COFs commonly used to enhance the separation of photogenerated electrons and holes at molecular level promoting migration towards acceptor movement donor. However, significantly slower kinetics synchronous water oxidation oxygen reduction reactions (WOR ORR) result in accumulation carriers, which induces strong Coulomb forces, turn adversely affecting efficiency D-A COFs. Herein, it is observed that keto-enol tautomerism can function as dynamic traps both holes, alternately capturing them, while counterpart participate consumed during asynchronous reactions. This represents first example T-C (T denotes units; C catalytic active units), effectively weaken force reducing accumulation, resulting rapid transfer prolonged lifetimes free carriers efficient alternating photocatalytic WOR ORR. Our in-depth research indicates imine based on 2,4,6-trihydroxybenzaldehyde-1,3,5-tricarbaldehyde (Tp series) exhibit enhanced activity compared those 1,3,5-benzenetricarboxaldehyde (BT series), be attributed occurrence tautomerization. Notably, optimal Tp COF (TpBpy) displays an ultrafast rate H2O2 reaching 3.79 mM h-1, surpassing all previously reported photocatalysts. More importantly, when employed a flow-reactor system, TpBpy also showcases exceptional effectiveness continuous synthesis, achieving solar-to-chemical conversion (SCC) 0.038%, representing highest performance recorded date under natural sunlight conditions. work offers molecular-level guidance designing photosynthesis proposes standardized criteria obtaining reliable SCC values.

Language: Английский

Direct Photocatalytic Oxidation of Methane to Formic Acid with High Selectivity via a Concerted Proton–Electron Transfer Process DOI
G.H. Zhai, Siyuan Yang, Yihong Chen

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 7, 2025

Light-driven direct conversion of methane to formic acid is a promising approach convert value-added chemicals and promote sustainability. However, this process remains challenging due the complex requirements for multiple protons electrons. Herein, we report design WO3-based photocatalysts modified with Pt active sites address challenge. We demonstrate that modulating dimensional effect on WO3 support key enhancing catalytic performance selective CH4-to-HCOOH conversion. The nanoparticles exhibit superior rate, selectivity durability in production HCOOH compared Pt-free sample decorated single atoms. optimal PtNPs-WO3 catalyst achieves rate 17.7 mmol g–1, 84% stability maintained up 48 h. Mechanistic studies show protonation O2 hydroxyl radicals limiting step yield. can facilitate electron transfer dissociation, generating via proton-coupled process. This provides sufficient lower formation barrier •OH radicals, thereby promoting activation CH4. In addition, regulate adsorption oxygenated hydrocarbon intermediates, increasing reaction. work advances our understanding effective regulation reaction pathways.

Language: Английский

Citations

1
Selective Photocatalytic Oxidative Ethane Dehydrogenation on AuPd Nanoparticle-Decorated TiO2 DOI
Xindan Zhang,

Jiale Shi,

Xiaoyan Wu

et al.

ACS Applied Materials & Interfaces, Journal Year: 2025, Volume and Issue: 17(9), P. 14119 - 14128

Published: Feb. 24, 2025

Photocatalytic oxidative dehydrogenation of ethane offers a promising approach for producing ethylene under mild conditions. However, achieving high yields and selectivity is challenging due to the C-H bond activation barrier in tendency overoxidation CO2. In this study, we demonstrate that TiO2 with highly dispersed AuPd nanoparticles serves as an efficient selective photocatalyst O2 flow reactor. The optimized Au0.33Pd0.67/TiO2 achieves up 20.3 mmol g-1 h-1 91.5% selectivity, resulting 5.9% apparent quantum efficiency at 365 nm. Detailed characterizations reveal Au0.33Pd0.67 cocatalyst plays crucial role facilitating photocarrier separation regulating formation active oxygen species. effectively activates lattice TiO2, which localized oxidant promote dissociation through photoassisted Mars-van Krevelen mechanism. Additionally, facilitates dioxygen reduction ensures rapid replenishment lattice, thereby yield formation. This work provides valuable insights designing composite photocatalysts dehydrogenation.

Language: Английский

Citations

1
Photocatalytic CH4-to-Ethanol Conversion on Asymmetric Multishelled Interfaces DOI
Shuya Hao,

Yuanyuan Xue,

Peng Chen

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(37), P. 25870 - 25877

Published: Sept. 4, 2024

The selective oxidation of methane (CH

Language: Английский

Citations

7
Accelerated Design of Dual-Metal-Site Catalysts via Machine-Learning Prediction DOI
Yang Wang, Qian Wang, Xijun Wang

et al.

The Journal of Physical Chemistry Letters, Journal Year: 2025, Volume and Issue: 16(6), P. 1424 - 1431

Published: Jan. 31, 2025

Dual-metal site catalysts (DMSCs) supported on nitrogen-doped graphene have shown great potential in heterogeneous catalysis due to their unique properties and enhanced efficiency. However, the precise control stabilization of metal dimers, particularly oxygen activation reactions, present significant challenges practical applications. In this study, we integrate high-throughput density functional theory calculations with machine learning techniques predict optimize catalytic DMSCs. Transfer is employed enhance model's generalization capability, successfully predicting performance across new combinations. Additionally, application SISSO method enables derivation interpretable symbolic regression models, revealing critical correlations between electronic structure features This approach not only advances understanding dual-metal but also provides a novel framework for systematic design optimization highly efficient catalysts, broad applicability science.

Language: Английский

Citations

0
[CrO4] Clusters as Dehydrogenation Terminators for Photocatalytic Oxidation of Methane to Achieve Nearly 100% Oxygenates Selectivity DOI
Zhengfeng Shen, Jianxin Liu, Lijun Guo

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 4824 - 4836

Published: March 7, 2025

Language: Английский

Citations

0
Insights into the Mechanism of Plasma Pretreatment-Enhanced Ammonia Decomposition Kinetics from a Lattice-Mediated Perspective DOI

Yuhui Du,

Junhui Liang, Xin Yao

et al.

Applied Catalysis A General, Journal Year: 2025, Volume and Issue: unknown, P. 120204 - 120204

Published: March 1, 2025

Language: Английский

Citations

0
Insights Into the Light‐Driven Conversion of Methane: Mechanisms, Characterization, and Perspective DOI Creative Commons
Jiayi Chen, Shiqin Gao, Tao Gan

et al.

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

Published: Feb. 26, 2025

ABSTRACT Methane, recognized as a promising substitute for conventional fossil fuels due to its abundant availability, low cost, and high energy density, can be converted into value‐added products, providing sustainable energy–carbon utilization approach. However, inert molecules require significant C–H bond activation. Photocatalytic conversion offers an effective mild‐condition solution, reducing thermocatalysis demands enhancing activation efficiency selective chemical production. This review systematically arranges photocatalytic mechanisms, categorizes discusses challenges, prospects, solutions methane photocatalysis development.

Language: Английский

Citations

0
Integrating photochemical and photothermal effects for selective oxidative coupling of methane into C2+ hydrocarbons with multiple active sites DOI Creative Commons
Hui Song, Kai Sun, Hengming Huang

et al.

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: March 22, 2025

The direct photocatalytic oxidation of methane to value-added chemicals has garnered considerable interest in recent years. However, achieving high productivity while maintaining selectivity at an appreciable conversion rate remains a formidable challenge. Here, we present photochemically-triggered and photothermally-enhanced oxidative coupling multi-carbon C2+ alkanes over Au CeO2 nanoparticle-decorated ZnO photocatalyst, which exhibits record-breaking production 17,260 μmol g−1 h−1 with ~90% under wide-spectrum light irradiation without secondary source heating. Comprehensive characterizations computational studies reveal that CH4 activation is photochemical reaction initiated by ultraviolet light-excited ZnO, the introduction substantially enhances O2 due cooperative interaction between CeO2. Concurrently, nanoparticles capture visible near-infrared generate localized heating, greatly promotes subsequent desorption produced methyl radical for C–C prior undergoing further undesired overoxidation. Achieving both activity photooxidation hydrocarbons challenging. This work shows integrating photothermal effects both, enabling efficient alkanes.

Language: Английский

Citations

0
Ag‐ZnO Nanoflowers Enable Highly Selective Photocatalytic Conversion of CH4 to CH3OH at Atmospheric Pressure: Unraveling Reactive Interfaces and Intermediate Control DOI Open Access

Boshi Zheng,

Yi Wan, Qi Hua

et al.

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

Published: March 21, 2025

At atmospheric pressure, the main challenge in photocatalytic oxidation of CH4 to CH3OH is absorb and activate inert C─H bond while preventing excessive CH3OH. In this study, metal-supported ZnO nanoflowers (Ag-ZnO) are designed produce abundant active interfacial oxygen sites for at with a yield reaching 1300 µmol gcat -1 h-1 selectivity 94%. DFT calculation situ analysis show that addition Ag regulates electron state density band center O, which beneficial adsorption CH4, decreases dissociation energy barrier OL(Lattice oxygen) site. The further selective conversion ·CH3 involves two different pathways: one pathway consists by OL, other combination ·OH generated from dissolved O2 (0.28 mm) water. Notably, photochemical flow device, increased 5200 close 100%. This work offers valuable insights into reactive interfaces, morphological engineering, control intermediate evolution toward oxygenates pressure.

Language: Английский

Citations

0
Revealing the Principle of Progressively Enhanced Photocatalytic Reactivity in Dual Single‐Atoms‐Mediated Electronic Interactions Optimization of Cd/Te‐TiO2 DOI Creative Commons
Yihang Zhang, Hao Zhao, Shan Jiang

et al.

Advanced Science, Journal Year: 2025, Volume and Issue: unknown

Published: March 17, 2025

Abstract In this work, a CdTe@TiO 2 single atoms (SAs) catalysts is successfully synthesized, realizing unique portion of nonbonding oxygen‐coordinated configuration Cd─O─Te dimers coupling. Astonishingly, the 5th (0.027 min −1 ) shows progressively augmenting phenomenon, accompanied with 2.73 times higher than that fresh (0.010 on photocatalytic rate constant gaseous toluene conversion. The incrementally enhanced activity attributed to atomically dispersed Cd/Te SAs sites generation during photoreduction process, and further leading optimized electron interactions between Cd, Te atoms, TiO NTs causing positive shift in d‐band center closer Fermi level. Density Functional Theory (DFT) calculations reveal increasing phenomenon can mutually elevate electronic density around generate substantial local electric field at interface. essence, free energy barriers benzene intermediates ring‐opening as rate‐determining step appeared significantly diminish tendency from 1.10 0.96 eV, line ICOHP calculation Cd/Te─O bonds TS promoted −2.43 −3.49 eV. This work unearths mechanism for ascendant states synergies dual‐metal sites, providing versatile strategy tailor solar

Language: Английский

Citations

0