Gas Phase Selective Oxidation of Methane to Formaldehyde

He Yan; Song Jiaxin; Fan Xiaoqiang; Yu Xuehua; Zhao Zhen

doi:10.7536/PC20250201

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Prog Chem ›› 2025, Vol. 37 ›› Issue (9) : 1321-1341. DOI: 10.7536/PC20250201

Review

Gas Phase Selective Oxidation of Methane to Formaldehyde

He Yan ¹ ,
Song Jiaxin ¹ ,
Fan Xiaoqiang ¹^,^* ,
Yu Xuehua ¹ ,
Zhao Zhen ¹^,²^,^*

Author information +

History +

Abstract

Methane， as a light alkane clean resource with abundant reserves， its efficient utilization has significant practical significance. Direct conversion of methane into high-value target products through gas-phase selective oxidation of methane has become an effective way to efficiently utilize methane. This reaction has the advantages of simple equipment and relatively low reaction energy consumption. However， the strong carbon-hydrogen bond of methane makes its activation process difficult， and the product formaldehyde is prone to deep oxidation under high-temperature and oxygen-containing conditions， resulting in a decrease in the selectivity of the target product. Therefore， achieving high-selectivity direct oxidation of methane to form oxygen-containing compounds is challenging. This article reviews the research progress in the gas-phase selective oxidation of methane to formaldehyde， focusing on the reaction mechanism of selective oxidation of methane to formaldehyde on catalysts， catalyst systems， and the application of various in-situ characterizations in the reaction. Finally， the future development directions of the selective oxidation of methane are summarized and prospected.

Contents

1 Introduction

2 Methane C―H bond activation

3 Reaction mechanism of gas phase selective oxidation of methane to formaldehyde

3.1 Mars-van Krevelen mechanism

3.2 Non‑Mars‑van Krevelen mechanism involving peroxide species

3.3 Langmuir‑Hinshelwood mechanism

4 Methane selective oxidation reaction catalyst system

4.1 Mo‑based catalyst

4.2 V‑based catalyst

4.3 Fe‑based catalyst

4.4 Other catalysts

5 In‑situ characterization of methane selective oxidation reaction

6 Conclusion and outlook

Key words

methane / gas-phase selective oxidation / formaldehyde / reaction mechanism / catalyst

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He Yan , Song Jiaxin , Fan Xiaoqiang , et al . Gas Phase Selective Oxidation of Methane to Formaldehyde[J]. Progress in Chemistry. 2025, 37(9): 1321-1341 https://doi.org/10.7536/PC20250201

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Funding

The National Natural Science Foundation of China(22172101)

The Applied Basic Research Program of Liaoning Province(2023JH2/101600059)

The "Xingliao Talents" Youth Top Talent Program of Liaoning Province(XLYC2203138)

The Special Fund for Basic Scientific Research and Operation of undergraduate universities in Liaoning Province(LJ212410166046)

The Major Project Incubation Project of Shenyang Normal University

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