Highly Selective Conversion of CH4 to High Value‐Added C1 Oxygenates over Pd Loaded ZnTi‐LDH DOI Creative Commons
Lei Fu, Ruixue Zhang, Jianlong Yang

et al.

Advanced Energy Materials, Journal Year: 2023, Volume and Issue: 13(29)

Published: June 19, 2023

Abstract The selective oxidation of methane to high value‐added liquid oxygenated compounds under mild conditions is great significance promote the efficient utilization carbon source, but it also faces dilemma low activity and over‐oxidation. Here, ZnTi‐layered double hydroxides (LDH)‐A200 photocatalysts with Pd loading are prepared achieve methane, O 2 as an oxidant ambient condition. highest generation rate C 1 products (methanol formaldehyde) reaches 4924.47 µmol g −1 h a selectivity close 100% over 0.5Pd‐ZnTi‐LDH‐A200, which 20 times higher than that bare ZnTi‐LDH‐A200. photochemical results show modified present much separation efficiency electron‐hole pairs. In situ X–ray photoelectron spectroscopy indicates nanoparticles hole acceptor, beneficial charge in photocatalysis. Furthermore, electron spinresonance temperature–programmed–desorption analysis prove helpful adsorption oxygen on surface ZnTi‐LDH‐A200, promoting production reactive species activation methane. All these factors work together conversion CH 4 oxygenates.

Language: Английский

Methane transformation by photocatalysis DOI
Xiyi Li, Chao Wang, Junwang Tang

et al.

Nature Reviews Materials, Journal Year: 2022, Volume and Issue: 7(8), P. 617 - 632

Published: Feb. 28, 2022

Language: Английский

Citations

252
Synergy of Pd atoms and oxygen vacancies on In2O3 for methane conversion under visible light DOI Creative Commons
Lei Luo, Lei Fu, Huifen Liu

et al.

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: May 25, 2022

Methane (CH4) oxidation to high value chemicals under mild conditions through photocatalysis is a sustainable and appealing pathway, nevertheless confronting the critical issues regarding both conversion selectivity. Herein, visible irradiation (420 nm), synergy of palladium (Pd) atom cocatalyst oxygen vacancies (OVs) on In2O3 nanorods enables superior photocatalytic CH4 activation by O2. The optimized catalyst reaches ca. 100 μmol h-1 C1 oxygenates, with selectivity primary products (CH3OH CH3OOH) up 82.5%. Mechanism investigation elucidates that such induced dedicated function Pd single atoms boosting hole electron transfer, respectively. O2 proven be only source for CH3OH production, while H2O acts as promoter efficient ·OH production facilitates product desorption indicated DFT modeling. This work thus provides new understandings simultaneous regulation activity cocatalysts vacancies.

Language: Английский

Citations

213
Efficient and selective photocatalytic CH4 conversion to CH3OH with O2 by controlling overoxidation on TiO2 DOI Creative Commons
Ningdong Feng, Huiwen Lin, Hui Song

et al.

Nature Communications, Journal Year: 2021, Volume and Issue: 12(1)

Published: Aug. 2, 2021

Abstract The conversion of photocatalytic methane into methanol in high yield with selectivity remains a huge challenge due to unavoidable overoxidation. Here, the oxidation CH 4 3 OH by O 2 is carried out on Ag-decorated facet-dominated TiO . {001}-dominated shows durable 4.8 mmol g −1 h and approximately 80%, which represent much higher values than those reported recent studies are better obtained for {101}-dominated Operando Fourier transform infrared spectroscopy, electron spin resonance, nuclear magnetic resonance techniques used comprehensively clarify underlying mechanism. straightforward generation oxygen vacancies {001} photoinduced holes plays key role avoiding formation •CH •OH, main factors leading overoxidation generally formed {101} facet. results distinct intermediates reaction pathways (oxygen vacancy → Ti–O • Ti–OO–Ti Ti–(OO) pairs), thus achieving photooxidation OH.

Language: Английский

Citations

204
Binary Au–Cu Reaction Sites Decorated ZnO for Selective Methane Oxidation to C1 Oxygenates with Nearly 100% Selectivity at Room Temperature DOI
Lei Luo,

Zhuyu Gong,

Youxun Xu

et al.

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 144(2), P. 740 - 750

Published: Dec. 20, 2021

Direct and efficient oxidation of methane to methanol the related liquid oxygenates provides a promising pathway for sustainable chemical industry, while still remaining an ongoing challenge owing dilemma between activation overoxidation. Here, ZnO with highly dispersed dual Au Cu species as cocatalysts enables selective photocatalytic conversion one-carbon (C1) using O2 oxidant operated at ambient temperature. The optimized AuCu-ZnO photocatalyst achieves up 11225 μmol·g-1·h-1 primary products (CH3OH CH3OOH) HCHO nearly 100% selectivity, resulting in 14.1% apparent quantum yield 365 nm, much higher than previous best photocatalysts reported oxygenates. In situ EPR XPS disclose that serve photoinduced electron mediators promote •OOH, simultaneously is hole acceptor enhance H2O •OH, thus synergistically promoting charge separation transformation. This work highlights significances co-modification suitable on simultaneous regulation activity selectivity.

Language: Английский

Citations

176
Oxo dicopper anchored on carbon nitride for selective oxidation of methane DOI Creative Commons
Pengfei Xie, Jing Ding, Zihao Yao

et al.

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: March 16, 2022

Selective conversion of methane (CH4) into value-added chemicals represents a grand challenge for the efficient utilization rising hydrocarbon sources. We report here dimeric copper centers supported on graphitic carbon nitride (denoted as Cu2@C3N4) advanced catalysts CH4 partial oxidation. The copper-dimer demonstrate high selectivity oxidation under both thermo- and photocatalytic reaction conditions, with hydrogen peroxide (H2O2) oxygen (O2) being used oxidizer, respectively. In particular, O2 achieves >10% conversion, >98% toward methyl oxygenates mass-specific activity 1399.3 mmol g Cu-1h-1. Mechanistic studies reveal that reactivity Cu2@C3N4 can be ascribed to symphonic mechanisms among bridging oxygen, two sites semiconducting C3N4 substrate, which do not only facilitate heterolytic scission C-H bond, but also promotes H2O2 activation in photocatalysis,

Language: Английский

Citations

172
Integration of redox cocatalysts for artificial photosynthesis DOI
Bocheng Qiu,

Mengmeng Du,

Yingxin Ma

et al.

Energy & Environmental Science, Journal Year: 2021, Volume and Issue: 14(10), P. 5260 - 5288

Published: Jan. 1, 2021

This review summarizes the design principle, emerging configurations, and photocatalytic applications of redox cocatalysts, offers insights perspectives on this topic.

Language: Английский

Citations

148
Nearly 100% selective and visible-light-driven methane conversion to formaldehyde via. single-atom Cu and Wδ+ DOI Creative Commons
Lei Luo, Xiaoyu Han,

Keran Wang

et al.

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: May 10, 2023

Direct solar-driven methane (CH4) reforming is highly desirable but challenging, particularly to achieve a value-added product with high selectivity. Here, we identify synergistic ensemble effect of atomically dispersed copper (Cu) species and partially reduced tungsten (Wδ+), stabilised over an oxygen-vacancy-rich WO3, which enables exceptional photocatalytic CH4 conversion formaldehyde (HCHO) under visible light, leading nearly 100% selectivity, very yield 4979.0 μmol·g-1 within 2 h, the normalised mass activity 8.5 × 106 μmol·g-1Cu·h-1 HCHO at ambient temperature. In-situ EPR XPS analyses indicate that Cu serve as electron acceptor, promoting photo-induced transfer from conduction band O2, generating reactive •OOH radicals. In parallel, adjacent Wδ+ act hole acceptor preferred adsorption activation site H2O produce hydroxyl radicals (•OH), thus activate methyl (•CH3). The synergy dual active sites boosts overall efficiency selectivity process.

Language: Английский

Citations

83
Asymmetrically coordinated cobalt single atom on carbon nitride for highly selective photocatalytic oxidation of CH4 to CH3OH DOI Creative Commons
Jie Ding, Zhenyuan Teng, Xiaozhi Su

et al.

Chem, Journal Year: 2023, Volume and Issue: 9(4), P. 1017 - 1035

Published: March 13, 2023

Language: Английский

Citations

65
High-density frustrated Lewis pairs based on Lamellar Nb2O5 for photocatalytic non-oxidative methane coupling DOI Creative Commons
Ziyu Chen,

Yutao Ye,

Xiaoyi Feng

et al.

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: April 10, 2023

Photocatalytic methane conversion requires a strong polarization environment composed of abundant activation sites with the robust stretching ability for C-H scissoring. High-density frustrated Lewis pairs consisting low-valence acid Nb and base Nb-OH are fabricated on lamellar Nb2O5 through thermal-reduction promoted phase-transition process. Benefitting from planar atomic arrangement Nb2O5, highly exposed accessible to reactants, which results in superior rate 1456 μmol g-1 h-1 photocatalytic non-oxidative coupling without assistance noble metals. The time-dependent DFT calculation demonstrates photo-induced electron transfer LA LB enhances their intensities concerted way, promoting cleavage LB. This work provides in-depth insight into designing constructing micro-environment

Language: Английский

Citations

43
Selective Photocatalytic Oxidation of Methane to Methanol by Constructing a Rapid O2 Conversion Pathway over Au–Pd/ZnO DOI
Qiang Zhou,

Xiaojie Tan,

Xinyu Wang

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(2), P. 955 - 964

Published: Jan. 5, 2024

Photocatalytic oxidation of methane to methanol is an attractive process under mild conditions, nevertheless confronting significant challenges in achieving high conversion and selectivity simultaneously. Herein, we propose a strategy for the direct rapid generation hydroxyl radicals (•OH) from O2 (O2 → *OOH •OH) by rational design Au–Pd/ZnO photocatalyst, skipping water-soluble H2O2 avoiding diffusion. For photocatalytic at ambient temperature, yield CH3OH over optimized 1.0% AuPd0.5/ZnO catalyst were as 81.0 μmol·h–1 88.2%, respectively, exceeding that most reported systems. The formation Au–Pd alloys could improve adsorption cleavage O–O bond *OOH, facilitating efficient •OH increasing selectivity. This work provides some guidance delicate composite photocatalysts selective utilization.

Language: Английский

Citations

33