Highly Selective Oxidation of Methane into Methanol over Cu-Promoted Monomeric Fe/ZSM-5

Tao Yu; Zhi Li; Lu Lin; Shengqi Chu; Yang Su; Weiyu Song; Aiqin Wang; Bert M. Weckhuysen; Wenhao Luo

doi:10.1021/acscatal.1c00905

Highly Selective Oxidation of Methane into Methanol over Cu-Promoted Monomeric Fe/ZSM-5

Tao Yu
, Zhi Li
, Lu Lin
, Shengqi Chu
, Yang Su
, Weiyu Song
, Aiqin Wang
, Bert M. Weckhuysen
, Wenhao Luo^*

^*Corresponding author for this work

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

Abstract

The selective oxidation of methane into methanol is of paramount importance but poses significant challenges in achieving high methanol productivity and selectivity, especially under mild reaction conditions. We show that a Cu-modified monomeric Fe/ZSM-5 catalyst is a highly efficient material for the direct conversion of methane into methanol in the liquid phase using H2O2 as an oxidant at low temperatures, which exhibits an excellent methanol productivity of 431 molMeOH·mol-1Fe·h-1 (with a methanol selectivity of μ80% over the Cu-Fe(2/0.1)/ZSM-5 catalyst). Combining the control experiments and comprehensive characterization results by among others, Mössbauer spectroscopy, and electron paramagnetic resonance as well as density functional theory calculations, we found that Cu species in the Cu-Fe(2/0.1)/ZSM-5 catalyst play a pivotal role in facilitating the formation of •OH radicals, which quickly react with •CH3 radicals to form CH3OH. These findings provide valuable insights into the rational design of metal-zeolite combinations for the selective oxidation of methane into methanol.

Original language	English
Pages (from-to)	6684-6691
Number of pages	8
Journal	ACS Catalysis
Volume	11
Issue number	11
DOIs	https://doi.org/10.1021/acscatal.1c00905
Publication status	Published - 4 Jun 2021

Bibliographical note

Funding Information:
Financial support for this work comes from the Strategic Priority Research Program of the Chinese Academy of Sciences (XDB17020100) and the Foundation of Dalian Institute of Chemical Physics (DICP I201915), which is gratefully acknowledged. We are also grateful for the support for X-ray absorption spectroscopy experiments from the Beijing Synchrotron Radiation Facility (BSRF).

Publisher Copyright:
© 2021 American Chemical Society.

Funding

Financial support for this work comes from the Strategic Priority Research Program of the Chinese Academy of Sciences (XDB17020100) and the Foundation of Dalian Institute of Chemical Physics (DICP I201915), which is gratefully acknowledged. We are also grateful for the support for X-ray absorption spectroscopy experiments from the Beijing Synchrotron Radiation Facility (BSRF).

Keywords

characterization
copper
methane
monomeric Fe species
zeolite

Access to Document

10.1021/acscatal.1c00905

acscatal.1c00905Final published version, 3.7 MBLicence: Taverne

Cite this

@article{1be8f2062e464410ab7f04176fae734e,

title = "Highly Selective Oxidation of Methane into Methanol over Cu-Promoted Monomeric Fe/ZSM-5",

abstract = "The selective oxidation of methane into methanol is of paramount importance but poses significant challenges in achieving high methanol productivity and selectivity, especially under mild reaction conditions. We show that a Cu-modified monomeric Fe/ZSM-5 catalyst is a highly efficient material for the direct conversion of methane into methanol in the liquid phase using H2O2 as an oxidant at low temperatures, which exhibits an excellent methanol productivity of 431 molMeOH·mol-1Fe·h-1 (with a methanol selectivity of μ80\% over the Cu-Fe(2/0.1)/ZSM-5 catalyst). Combining the control experiments and comprehensive characterization results by among others, M{\"o}ssbauer spectroscopy, and electron paramagnetic resonance as well as density functional theory calculations, we found that Cu species in the Cu-Fe(2/0.1)/ZSM-5 catalyst play a pivotal role in facilitating the formation of •OH radicals, which quickly react with •CH3 radicals to form CH3OH. These findings provide valuable insights into the rational design of metal-zeolite combinations for the selective oxidation of methane into methanol. ",

keywords = "characterization, copper, methane, monomeric Fe species, zeolite",

author = "Tao Yu and Zhi Li and Lu Lin and Shengqi Chu and Yang Su and Weiyu Song and Aiqin Wang and Weckhuysen, \{Bert M.\} and Wenhao Luo",

note = "Funding Information: Financial support for this work comes from the Strategic Priority Research Program of the Chinese Academy of Sciences (XDB17020100) and the Foundation of Dalian Institute of Chemical Physics (DICP I201915), which is gratefully acknowledged. We are also grateful for the support for X-ray absorption spectroscopy experiments from the Beijing Synchrotron Radiation Facility (BSRF). Publisher Copyright: {\textcopyright} 2021 American Chemical Society.",

year = "2021",

month = jun,

day = "4",

doi = "10.1021/acscatal.1c00905",

language = "English",

volume = "11",

pages = "6684--6691",

journal = "ACS Catalysis",

issn = "2155-5435",

publisher = "American Chemical Society",

number = "11",

}

TY - JOUR

T1 - Highly Selective Oxidation of Methane into Methanol over Cu-Promoted Monomeric Fe/ZSM-5

AU - Yu, Tao

AU - Li, Zhi

AU - Lin, Lu

AU - Chu, Shengqi

AU - Su, Yang

AU - Song, Weiyu

AU - Wang, Aiqin

AU - Weckhuysen, Bert M.

AU - Luo, Wenhao

N1 - Funding Information: Financial support for this work comes from the Strategic Priority Research Program of the Chinese Academy of Sciences (XDB17020100) and the Foundation of Dalian Institute of Chemical Physics (DICP I201915), which is gratefully acknowledged. We are also grateful for the support for X-ray absorption spectroscopy experiments from the Beijing Synchrotron Radiation Facility (BSRF). Publisher Copyright: © 2021 American Chemical Society.

PY - 2021/6/4

Y1 - 2021/6/4

N2 - The selective oxidation of methane into methanol is of paramount importance but poses significant challenges in achieving high methanol productivity and selectivity, especially under mild reaction conditions. We show that a Cu-modified monomeric Fe/ZSM-5 catalyst is a highly efficient material for the direct conversion of methane into methanol in the liquid phase using H2O2 as an oxidant at low temperatures, which exhibits an excellent methanol productivity of 431 molMeOH·mol-1Fe·h-1 (with a methanol selectivity of μ80% over the Cu-Fe(2/0.1)/ZSM-5 catalyst). Combining the control experiments and comprehensive characterization results by among others, Mössbauer spectroscopy, and electron paramagnetic resonance as well as density functional theory calculations, we found that Cu species in the Cu-Fe(2/0.1)/ZSM-5 catalyst play a pivotal role in facilitating the formation of •OH radicals, which quickly react with •CH3 radicals to form CH3OH. These findings provide valuable insights into the rational design of metal-zeolite combinations for the selective oxidation of methane into methanol.

AB - The selective oxidation of methane into methanol is of paramount importance but poses significant challenges in achieving high methanol productivity and selectivity, especially under mild reaction conditions. We show that a Cu-modified monomeric Fe/ZSM-5 catalyst is a highly efficient material for the direct conversion of methane into methanol in the liquid phase using H2O2 as an oxidant at low temperatures, which exhibits an excellent methanol productivity of 431 molMeOH·mol-1Fe·h-1 (with a methanol selectivity of μ80% over the Cu-Fe(2/0.1)/ZSM-5 catalyst). Combining the control experiments and comprehensive characterization results by among others, Mössbauer spectroscopy, and electron paramagnetic resonance as well as density functional theory calculations, we found that Cu species in the Cu-Fe(2/0.1)/ZSM-5 catalyst play a pivotal role in facilitating the formation of •OH radicals, which quickly react with •CH3 radicals to form CH3OH. These findings provide valuable insights into the rational design of metal-zeolite combinations for the selective oxidation of methane into methanol.

KW - characterization

KW - copper

KW - methane

KW - monomeric Fe species

KW - zeolite

UR - https://www.scopus.com/pages/publications/85108819071

U2 - 10.1021/acscatal.1c00905

DO - 10.1021/acscatal.1c00905

M3 - Article

AN - SCOPUS:85108819071

SN - 2155-5435

VL - 11

SP - 6684

EP - 6691

JO - ACS Catalysis

JF - ACS Catalysis

IS - 11

ER -

Highly Selective Oxidation of Methane into Methanol over Cu-Promoted Monomeric Fe/ZSM-5

Abstract

Bibliographical note

Funding

Keywords

Access to Document

Other files and links

Fingerprint

Cite this