Direct Photocatalytic Oxidation of Methane to Formic Acid with High Selectivity via a Concerted Proton–Electron Transfer Process

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Янв. 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.

Язык: Английский

---

Photocatalytic CH₄-to-Ethanol Conversion on Asymmetric Multishelled Interfaces

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(37), С. 25870 - 25877

Опубликована: Сен. 4, 2024

The selective oxidation of methane (CH

Язык: Английский

---

Titanium in photocatalytic organic transformations: current applications and future developments

Organic & Biomolecular Chemistry, Год журнала: 2024, Номер 22(33), С. 6650 - 6664

Опубликована: Янв. 1, 2024

Titanium, as an important transition metal, has garnered extensive attention in both industry and academia due to its excellent mechanical properties, corrosion resistance, unique reactivity organic synthesis. In the field of photocatalysis, titanium-based compounds such titanium dioxide (TiO

Язык: Английский

---

Largely Promoted C–H Activation in Methane with O₂ via d-Orbital Hybridization Induced by CuO_x Supported on ZnO

ACS Catalysis, Год журнала: 2025, Номер 15(3), С. 1607 - 1615

Опубликована: Янв. 15, 2025

Efficiently converting methane (CH4) to C1 products such as CH3OH, HCHO, and CH3OOH is considered a promising route for the chemical industry, while huge challenge of low CH4 activation rate still remains. Here, Cu/ZnO composite catalyst with CuOx supported on ZnO synthesized modify electronic structure utilized conversion. The fast e– transfer channel → Cu O2 facilitates dissociation •OOH, which promotes charge separation and, in parallel, enables oxidation •CH3 by h+ left acceleration effect situ generated •OOH. Mechanistic studies revealed that additional d-π*/d-σ-orbital hybridization between adsorbed O2/CH4 molecules plays decisive roles activation, resulted highest signal, so far we know, ultimately remarkably high yield 21.25 mmol g–1 h–1 100% selectivity over optimized 1 wt % photocatalyst. This work offers valuable guidance designation conversion presence O2.

Язык: Английский

---

Synergetic Atom‐Island and Metal Alloy Triggering Tandem Reaction for CH₄ Photooxidation to CH₃OH

Advanced Functional Materials, Год журнала: 2025, Номер unknown

Опубликована: Янв. 28, 2025

Abstract CH 3 OH is the most desired product of photocatalytic 4 conversion. The prominent metal‐decorated photocatalyst challenging in both high yield and selectivity for products due to over‐oxidation by •OH mechanism. Here, interstitial Zn fabricated into i O induce formation atom island rapid single electron reduction 2 •OOH instead selective combination with methyl OOH. AuPd alloy simultaneously decorated on surface tuning OOH adsorption OH. synergy achieve a tandem reaction pathway (CH →CH OOH→CH OH) an unprecedented 2444 mmol g −1 h (or 8800 µmol cat ) 98.3% selectivity, which bypasses mechanism An apparent quantum efficiency 18.53% at 370 nm conversion are super reported systems. Thus, this work provides new strategy synergetic metal photocatalysts through mediate oxidation

Язык: Английский

---

Selective Photocatalytic Aerobic Oxidation of Methane to Methyl Hydroperoxide by ZnO-Loaded Single-Atomic Ruthenium Oxide Catalyst

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Фев. 27, 2025

Photooxidation of CH4 to value-added chemicals with high selectivity offers a promising pathway drive the rational utilization natural gas resources renewable energy under mild conditions. However, owing poor chemoselectivity reactive oxygen radical formation and consecutive side reactions primary products, synthesis peroxide directly from oxidation remains challenging. Here, we report single-atom ruthenium oxide-doped ZnO as highly selective photocatalyst for aerobic CH3OOH. Under optimal conditions, CH3OOH rate over Ru1Ox/ZnO reaches 321 μmol gcat–1 h–1 90.9% simulated solar irradiation. Mechanistic studies reveal that generation •OOH radicals via reduction ability prevent secondary are main advantages Ru1Ox/ZnO, accounting remarkable CH4. The Ru oxide/ZnO catalyst also exhibits alkyl hydroperoxide in photocatalytic low paraffins, which provides solution prepare single-step hydrocarbon substrates.

Язык: Английский

---

Cu-based Bimetallic Catalysts for Electrochemical CO2 Reduction: Before and Beyond the Tandem Effect

Nanoscale, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

Cu-based bimetallic catalysts show enhanced electrochemical CO 2 reduction performance via the tandem effect. This review traces their progress, highlighting design advances, mechanisms, and challenges to guide efficient conversion.

Язык: Английский

---

Insights Into the Light‐Driven Conversion of Methane: Mechanisms, Characterization, and Perspective

EcoEnergy, Год журнала: 2025, Номер unknown

Опубликована: Фев. 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.

Язык: Английский

---

Ag-Mg tandem sites co-modified ultrathin ZnO achieving adsorption and activation synergistic effects for light–driven methane selective conversion

Chemical Engineering Journal, Год журнала: 2025, Номер unknown, С. 162380 - 162380

Опубликована: Апрель 1, 2025

Язык: Английский

---

Core–Shell MIL-125-NH₂@FeOOH Nanocomposites for Highly Selective Photocatalytic Oxidation of Methane to Formaldehyde in Water Vapor

Inorganic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Апрель 21, 2025

Formaldehyde (HCHO), a crucial industrial chemical, finds extensive applications across diverse sectors, including household products, commercial materials, aviation, and medical supplies. Methane (CH4), as an abundant C1 resource, presents promising feedstock for HCHO synthesis. However, the direct conversion of CH4 to remains challenging due its inherent chemical inertness, characterized by low polarizability high C-H bond dissociation energy (439 kJ mol-1), coupled with reactivity intermediate products. The development efficient strategies selective oxidation high-value under mild conditions is therefore significant practical importance. In this study, we developed series MIL-125-NH2@FeOOH-x heterostructured photocatalysts (FM-x) through controlled deposition FeOOH nanoparticles on MIL-125-NH2 surfaces. Comprehensive characterization photocatalytic evaluations reveal that optimized FM-1 catalyst facilitates in situ H2O2 generation subsequent decomposition into hydroxyl radicals (•OH), enabling photooxidation. Remarkably, achieves exceptional production rate 197.79 μmol·gcat-1 >99.99% selectivity water vapor, significantly outperforming both pristine components. This work system conversion, offering new insights design catalysts chemistry.

Язык: Английский

---