Unconventional Carrier Transfer Enabled Direct O2 Reduction by Oxygen Vacancies for Efficient Photooxidation of CH4 DOI
Yingdong Hao,

Yonghui Zhao,

Jun Ma

et al.

ACS Applied Materials & Interfaces, Journal Year: 2025, Volume and Issue: unknown

Published: May 8, 2025

Photocatalytic oxidation of methane (CH4) to high value-added liquid oxygenates with oxygen (O2) as an oxidant has long been a promising process. In addition the activation CH4, selective reduction O2 hydroperoxyl (·OOH) is also crucial factor in determining efficiency and selectivity overall reaction. thermal catalysis, strong interactions between vacancies (OVs) on catalyst surface are widely adopted means enhancing activation. However, reports this phenomenon limited photocatalysis; attributable fact that dependent upon its reaction photogenerated electrons (e-). For majority photocatalysts, transfer e- metal cocatalysts results spatial separation from OVs. Therefore, intrinsic affinity OVs not fully exploited. study, we discovered H2 treatment at elevated temperatures ZIF-8-derived ZnO led formation OV-enriched amorphous layer surface. After introduction Ag cocatalyst, as-prepared Agx-OVs/ZnO exhibited unconventional carrier direction, whereby holes (h+) transferred Ag, respectively. As result, preferential adsorption sites can be spatially combined together thus drive realize efficient directed generation ·OOH. parallel, h+ weakens capability avoids overoxidation while ensuring CH4 The optimized defect-rich Ag0.5-OVs/ZnO-z photocatalyst reaches oxygenate yield 10148 μmol gcat-1 h-1 95% TOF 2.4 × 106 gAg-1 h-1. This work sheds new light design photocatalytic catalysts via manipulation direction.

Language: Английский

Photodriven Methane Conversion on Transition Metal Oxide Catalyst: Recent Progress and Prospects DOI Creative Commons
Pu Wang, Run Shi, Jiaqi Zhao

et al.

Advanced Science, Journal Year: 2023, Volume and Issue: 11(8)

Published: Oct. 26, 2023

Methane as the main component in natural gas is a promising chemical raw material for synthesizing value-added chemicals, but its harsh conversion process often causes severe energy and environment concerns. Photocatalysis provides an attractive path to active convert methane into various products under mild conditions with clean sustainable solar energy, although many challenges remain at present. In this review, recent advances photocatalytic are systematically summarized. As basis of conversion, activation first elucidated from structural molecules. The study committed categorizing elucidating research progress laws intricate reactions according target products, including partial oxidation, reforming, coupling, combustion, functionalization. Advanced reactor designs also designed enrich options reliability performance evaluation. prospects discussed, which turn offers guidelines methane-conversion-related photocatalyst exploration, reaction mechanism investigation, advanced photoreactor design.

Language: Английский

Citations

44
Modulating Adsorption–Redox Sites and Charge Separation of Cs3Bi2Br9–x@AgBr Core–Shell Heterostructure for Selective Toluene Photooxidation DOI
Biao Zhou, Kezhou Fan,

Yanan Chong

et al.

ACS Energy Letters, Journal Year: 2024, Volume and Issue: 9(4), P. 1743 - 1752

Published: March 26, 2024

Constructing vacancy-decorated heterojunction photocatalysts is a feasible strategy for highly efficient photooxidation of toluene to benzaldehyde. However, poor interface interaction and vacancy-triggered mismatched redox kinetics seriously impede photocatalytic activity improvement. Herein, chemically bonded Cs3Bi2Br9–x@AgBr core–shell with unified adsorption-redox sites fabricated via an in-situ light-assisted Ag+ insertion method. Experiments theoretical calculations demonstrate that the type-II band alignment interfacial Bi–Br–Ag bonds boosts charge separation. Moreover, because greater oxygen adsorption energy steric-hindrance effect AgBr shell, preferred site O2 modulated from Br vacancy (VBr, trapping holes) its corresponding reduction (AgBr, gathering electrons), thereby ensuring VBr-enhancing adsorption/oxidation on Cs3Bi2Br9. Therefore, exhibits improved benzaldehyde production rate 5.61 mmol g–1 h–1 (selectivity: 91%), outperforming pure Cs3Bi2Br9 by factor 6. This work underlines importance rational design heterointerface at atomic level in photocatalysis.

Language: Английский

Citations

22
Highly efficient, selective, and stable photocatalytic methane coupling to ethane enabled by lattice oxygen looping DOI Creative Commons
G.H. Zhai, Lejuan Cai, Jun Ma

et al.

Science Advances, Journal Year: 2024, Volume and Issue: 10(26)

Published: June 28, 2024

Light-driven oxidative coupling of methane (OCM) for multi-carbon (C

Language: Английский

Citations

19
Recent advances on aerobic photocatalytic methane conversion under mild conditions DOI
Yuheng Jiang, Siyang Li, Xiaoyu Fan

et al.

Nano Research, Journal Year: 2023, Volume and Issue: 16(11), P. 12558 - 12571

Published: Oct. 31, 2023

Language: Английский

Citations

29
Photocatalytic production of ethylene and propionic acid from plastic waste by titania-supported atomically dispersed Pd species DOI Creative Commons
Shuai Zhang, Bingquan Xia, Yang Qu

et al.

Science Advances, Journal Year: 2023, Volume and Issue: 9(49)

Published: Dec. 8, 2023

Current chemical recycling of bulk synthetic plastic, polyethylene (PE), operates at high temperature/pressure and yields a complex mixture products. PE conversion under mild conditions with good selectivity toward value-added chemicals remains practical challenge. Here, we demonstrate an atomic engineering strategy to modify TiO 2 photocatalyst reversible Pd species for the selective ethylene (C H 4 ) propionic acid via dicarboxylic intermediates moderate conditions. -supported atomically dispersed exhibits C evolution 531.2 μmol g cat −1 hour , 408 times that pristine . The liquid product is valuable propanoic 98.8% selectivity. Plastic hydrocarbon yield 0.9% 6.3% was achieved in oxidation coupled 3 hours photoreaction. In situ spectroscopic studies confirm dual role species: electron acceptor boost charge separation/transfer efficient photoredox, mediator stabilize reaction decarboxylation.

Language: Английский

Citations

29
Steering Photooxidation of Methane to Formic Acid over A Priori Screened Supported Catalysts DOI
Yuheng Jiang, Yingying Fan, Xiaolong Liu

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(23), P. 16039 - 16051

Published: June 4, 2024

Efficient methane photooxidation to formic acid (HCOOH) has emerged as a sustainable approach simultaneously generate value-added chemicals and harness renewable energy. However, the persistent challenge lies in achieving high yield selectivity for HCOOH formation, primarily due complexities associated with modulating intermediate conversion desorption after activation. In this study, we employ first-principles calculations comprehensive guiding tool discover that by precisely controlling O2 activation process on noble metal cocatalysts adsorption strength of carbon-containing intermediates oxide supports, one can finely tune products. Specifically, bifunctional catalyst comprising Pd nanoparticles monoclinic WO3 (Pd/WO3) would possess optimal kinetics an oxidation/desorption barrier, thereby promoting formation. As evidenced experiments, Pd/WO3 achieves exceptional 4.67 mmol gcat–1 h–1 62% under full-spectrum light irradiation at room temperature using molecular O2. Notably, these results significantly outperform state-of-the-art photocatalytic systems operated identical condition.

Language: Английский

Citations

16
Directional Activation of Oxygen by the Au‐Loaded ZnAl‐LDH with Defect Structure for Highly Efficient Photocatalytic Oxidative Coupling of Methane DOI

Xiaoliang Sun,

Guihao Liu,

Tianyang Shen

et al.

Small, Journal Year: 2024, Volume and Issue: 20(28)

Published: Feb. 13, 2024

Abstract Photocatalytic oxidative coupling of CH 4 (OCM) is a promising conversion process that can achieve efficient methane with the assistance O 2 . It remains to be highly challenging improve photocatalytic OCM activity from catalyst design and deepen understanding reactant activation in process. In this work, Au‐loaded ZnAl‐layered double hydroxides (LDHs) without oxygen vacancy are constructed (denoted as Au/ZnAl Au/ZnAl‐v), respectively. When applied for OCM, Au/ZnAl‐v shows rate 8.5 mmol g −1 h 92% selectivity C H 6 at 40 °C, outperforming most reported systems low temperature literature. Furthermore, catalytic performance stable 100 h. contrast, An/ZnAl exhibits 0.8 46% Detailed characterizations DFT calculation studies reveal introduced Ov sites on able activate , resulting superoxide radical · − greatly promotes The 3 groups Au cocatalyst leads formation high activity.

Language: Английский

Citations

11
Nitrogen-Doped Titanium Dioxide for Selective Photocatalytic Oxidation of Methane to Oxygenates DOI
Guanghui Feng, Jianing Mao, Tong Sun

et al.

ACS Applied Materials & Interfaces, Journal Year: 2024, Volume and Issue: 16(4), P. 4600 - 4605

Published: Jan. 19, 2024

Photocatalytic conversion of methane (CH4) to value-added chemicals using H2O as the oxidant under mild conditions is a desired sustainable pathway for synthesizing commodity chemicals. However, controlling product selectivity while maintaining high yields greatly challenging. Herein, we develop highly efficient strategy, based on precise control types nitrogen dopants, and design photocatalysts, achieve productivity oxygenates via CH4 photocatalytic conversion. The primary (methanol) obtained in yield 159.8 μmol·g–1·h–1 47.7% selectivity, oxygenate compounds reached 92.5%. unique hollow porous structure substituted sites nitrogen-doped TiO2 synergistically promote its photo-oxidation performance. Furthermore, situ attenuated total reflectance Fourier transform infrared spectroscopy provides direct evidence key intermediates their evolution producing methanol multicarbon oxygenates. This study insights into mechanism

Language: Английский

Citations

10
Selective oxidation of methane to C2+ products over Au-CeO2 by photon-phonon co-driven catalysis DOI Creative Commons
Chao Wang, Youxun Xu, Lunqiao Xiong

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Aug. 30, 2024

Direct methane conversion to high-value chemicals under mild conditions is attractive yet challenging due the inertness of and high reactivity valuable products. This work presents an efficient selective strategy achieve direct through oxidative coupling over a visible-responsive Au-loaded CeO

Language: Английский

Citations

10
Photocatalytic Conversion of Methane to Ethanol at a Three-Phase Interface with Concentration-Matched Hydroxyl and Methyl Radicals DOI

Chun Ju He,

Lan Shang,

Hongfu Zhu

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(17), P. 11968 - 11977

Published: April 17, 2024

The direct oxidation of CH4 to C2H5OH is attractive but challenging owing the intricate processes involving carbon-chain growth and hydroxylation simultaneously. inherent difficulty arises from strong tendency overoxidize in commonly used pressurized powder suspension systems rich reactive oxygen radicals (ROR), which are specifically designed for concentration activation. Meanwhile, nucleophilic attack potent ROR on C–C bond resulting product ultimately leads a higher selectivity C1 oxygenates. This study addresses this multifaceted issue by designing three-phase interface based hydrophilic floating Fe(III)-cross-linked macroporous alginate hydrogel film encapsulated with C3N4 [Fe(III)@ACN] simultaneously enhance accessibility H2O molecules active sites species within channel. properties Fe(III)@ACN allow situ production H2O2 through water reaction under irradiation. concurrent photoinduced Fe(II) triggers Fenton produce •OH. enhanced mass transfer at ensures efficient formation •CH3 reacting •OH, facilitating conversion pathway CH3OH finally •OH present comparable concentrations. Thus, catalyst exhibits remarkable 96% alcohol, achieving 90% alcohol products. rate reaches 171.7 μmol g–1 h–1 without need precious-metal additive.

Language: Английский

Citations

9