Fe binuclear sites convert methane to acetic acid with ultrahigh selectivity

Bo Wu; Tiejun Lin; Zhengxing Lu; Xing Yu; Min Huang; Ruoou Yang; Caiqi Wang; Chen Tian; Jiong Li; Yuhan Sun; Liangshu Zhong

doi:10.1016/j.chempr.2022.02.001

Fe binuclear sites convert methane to acetic acid with ultrahigh selectivity

Bo Wu
, Tiejun Lin
, Zhengxing Lu
, Xing Yu
, Min Huang
, Ruoou Yang
, Caiqi Wang
, Chen Tian
, Jiong Li
, Yuhan Sun
, Liangshu Zhong

Surface Chemistry & Catalysis Group

Research output: Contribution to journal › Article › peer-review

81 Scopus citations

Abstract

The direct conversion of methane to C2 oxygenates with high selectivity under mild conditions has attracted wide attention but still remains a great challenge. Herein, we report the conversion of methane to acetic acid (CH₃COOH) with ultrahigh selectivity for oxygenated products by the direct coupling of CH₄, CO, and H₂O₂ over ZSM-5-supported Fe binuclear sites under 30°C. The unexpected ultrahigh selectivity toward CH₃COOH was attributed to the unique Fe binuclear site structure of [Fe(III)–(μO)₂–Fe(III)–(OH)₂], which was evidenced by advanced spectroscopic techniques and density functional theory (DFT) calculations. It was suggested that the lower energy barriers for the direct coupling of methyl radicals (·CH₃) and adsorbed CO∗ and OH∗ species to form CH₃COOH, compared with the oxidation of CH₄ by OH∗ to form CH₃OH, benefited the CH₃COOH formation.

Original language	English
Pages (from-to)	1658-1672
Number of pages	15
Journal	Chem
Volume	8
Issue number	6
DOIs	https://doi.org/10.1016/j.chempr.2022.02.001
State	Published - Jun 9 2022

Funding

This work was supported by Natural Science Foundation of China ( 91945301 ), National Key R&D Program of China ( 2021YFF0500702 ), Program of Shanghai Academic/Technology Research Leader ( 20XD1404000 ), Key Research Program of Frontier Sciences of the Chinese Academy of Sciences (grant no. QYZDB-SSW-SLH035 ), the “ Transformational Technologies for Clean Energy and Demonstration ” and Strategic Priority Research Program of CAS (grant No. XDA21020600 ) and the Youth Innovation Promotion Association of CAS .

Keywords

acetic acid
binuclear sites
C–C coupling
Fe
methane
SDG7:Affordable and clean energy

Access to Document

10.1016/j.chempr.2022.02.001

Cite this

@article{4bb8af88cc544e65ba840e546a5b96da,

title = "Fe binuclear sites convert methane to acetic acid with ultrahigh selectivity",

abstract = "The direct conversion of methane to C2 oxygenates with high selectivity under mild conditions has attracted wide attention but still remains a great challenge. Herein, we report the conversion of methane to acetic acid (CH3COOH) with ultrahigh selectivity for oxygenated products by the direct coupling of CH4, CO, and H2O2 over ZSM-5-supported Fe binuclear sites under 30°C. The unexpected ultrahigh selectivity toward CH3COOH was attributed to the unique Fe binuclear site structure of [Fe(III)–(μO)2–Fe(III)–(OH)2], which was evidenced by advanced spectroscopic techniques and density functional theory (DFT) calculations. It was suggested that the lower energy barriers for the direct coupling of methyl radicals (·CH3) and adsorbed CO∗ and OH∗ species to form CH3COOH, compared with the oxidation of CH4 by OH∗ to form CH3OH, benefited the CH3COOH formation.",

keywords = "acetic acid, binuclear sites, C–C coupling, Fe, methane, SDG7:Affordable and clean energy",

author = "Bo Wu and Tiejun Lin and Zhengxing Lu and Xing Yu and Min Huang and Ruoou Yang and Caiqi Wang and Chen Tian and Jiong Li and Yuhan Sun and Liangshu Zhong",

note = "Publisher Copyright: {\textcopyright} 2022 Elsevier Inc.",

year = "2022",

month = jun,

day = "9",

doi = "10.1016/j.chempr.2022.02.001",

language = "English",

volume = "8",

pages = "1658--1672",

journal = "Chem",

issn = "2451-9308",

publisher = "Cell Press",

number = "6",

}

TY - JOUR

T1 - Fe binuclear sites convert methane to acetic acid with ultrahigh selectivity

AU - Wu, Bo

AU - Lin, Tiejun

AU - Lu, Zhengxing

AU - Yu, Xing

AU - Huang, Min

AU - Yang, Ruoou

AU - Wang, Caiqi

AU - Tian, Chen

AU - Li, Jiong

AU - Sun, Yuhan

AU - Zhong, Liangshu

PY - 2022/6/9

Y1 - 2022/6/9

N2 - The direct conversion of methane to C2 oxygenates with high selectivity under mild conditions has attracted wide attention but still remains a great challenge. Herein, we report the conversion of methane to acetic acid (CH3COOH) with ultrahigh selectivity for oxygenated products by the direct coupling of CH4, CO, and H2O2 over ZSM-5-supported Fe binuclear sites under 30°C. The unexpected ultrahigh selectivity toward CH3COOH was attributed to the unique Fe binuclear site structure of [Fe(III)–(μO)2–Fe(III)–(OH)2], which was evidenced by advanced spectroscopic techniques and density functional theory (DFT) calculations. It was suggested that the lower energy barriers for the direct coupling of methyl radicals (·CH3) and adsorbed CO∗ and OH∗ species to form CH3COOH, compared with the oxidation of CH4 by OH∗ to form CH3OH, benefited the CH3COOH formation.

AB - The direct conversion of methane to C2 oxygenates with high selectivity under mild conditions has attracted wide attention but still remains a great challenge. Herein, we report the conversion of methane to acetic acid (CH3COOH) with ultrahigh selectivity for oxygenated products by the direct coupling of CH4, CO, and H2O2 over ZSM-5-supported Fe binuclear sites under 30°C. The unexpected ultrahigh selectivity toward CH3COOH was attributed to the unique Fe binuclear site structure of [Fe(III)–(μO)2–Fe(III)–(OH)2], which was evidenced by advanced spectroscopic techniques and density functional theory (DFT) calculations. It was suggested that the lower energy barriers for the direct coupling of methyl radicals (·CH3) and adsorbed CO∗ and OH∗ species to form CH3COOH, compared with the oxidation of CH4 by OH∗ to form CH3OH, benefited the CH3COOH formation.

KW - acetic acid

KW - binuclear sites

KW - C–C coupling

KW - Fe

KW - methane

KW - SDG7:Affordable and clean energy

UR - https://www.scopus.com/pages/publications/85132021346

U2 - 10.1016/j.chempr.2022.02.001

DO - 10.1016/j.chempr.2022.02.001

M3 - Article

AN - SCOPUS:85132021346

SN - 2451-9308

VL - 8

SP - 1658

EP - 1672

JO - Chem

JF - Chem

IS - 6

ER -

Fe binuclear sites convert methane to acetic acid with ultrahigh selectivity

Abstract

Funding

Keywords

Access to Document

Other files and links

Fingerprint

Cite this