In-situ synthesis of hydrogen peroxide for highly selective oxidation of methane to methanol over noble-metal-free catalyst

doi:10.1016/S1872-2067(26)65141-8

Abstract

Abstract:

Hydroxyl radicals (•OH) are crucial in the photocatalytic oxidation of methane (CH₄) to methanol (CH₃OH) at room temperature. Hydrogen peroxide (H₂O₂) is generally employed to drive CH₄ oxidation by providing •OH radicals; however, its practice use is often limited by high cost and handling challenges. Here we report a Zr-based metal-organic framework material modified by amino groups (U-NH₂), which severs as a noble-metal-free catalyst enabling visible light absorption and electron density redistribution. The U-NH₂ catalyst performs outstanding in-situ photosynthesis of H₂O₂ with O₂ under visible light in a sacrificial-agent-free system, achieving an H₂O₂ yield up to 189 µmol g^-1. Molecular dynamics simulations reveal that O₂ preferentially accumulates near the amino-functionalized pores of U-NH₂, creating localized O₂-enriched microenvironments that are critical for efficient H₂O₂ synthesis. The in situ synthesized H₂O₂ promotes the generation of •OH radicals, driving CH₄ oxidation to CH₃OH. Remarkably, highly selective generation of CH₃OH is achieved with a selectivity of near 100% and a yield of up to 412 mL g_cat^-1 per concentration of H₂O₂. Our finding opens up an appealing avenue for efficient solar energy activation of CH₄ to generate CH₃OH at ambient temperatures.

Key words: Methane, Methanol, Selectivity, Oxidation, Hydrogen peroxide

Songling Wang, Anhua Huang, Fengxing Yin, Ruixiang Lu, Wengang Liu, Yun Zhang, Botao Qiao. In-situ synthesis of hydrogen peroxide for highly selective oxidation of methane to methanol over noble-metal-free catalyst[J]. Chinese Journal of Catalysis, 2026, 88: 347-355.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65141-8

https://www.cjcatal.com/EN/Y2026/V88/I9/347

Figures/Tables 7

Fig. 1. Schematic reaction processes of in-situ synthesis of H2O2 and conversion of methane to methanol with solar light.

Fig. 2. Structural characterizations of U, U-NO2, and U-NH2 materials. (a) Schematic synthesis. (b) XRD patterns. (c) FTIR spectra. High-resolution XPS spectra of N 1s (d) and C 1s (e).

Fig. 3. Optical properties and electronic band structure of U, U-NO2, and U-NH2 materials. (a) UV-Vis DRS absorbance spectra. (b) Plots obtained using the Kubelka-Munk function transformation for the calculated absorbance versus the photon energy. (c) Mott-Schottky plots examined by a three-electrodes system without light irradiation. (d) Band energy diagram and redox potentials of O2/H2O2 and H2O2/H2O.

Fig. 4. Characterizations and photocatalytic activity under visible light irradiation of U, U-NO2, and U-NH2 materials. (a) Photocurrent detection. (b) EIS. (c) Generation yield of H2O2 with reaction time. (d) Photo-oxidative performance of CH4. (e) Stability test of photo-oxidative activity of methane to methanol product over U-NH2 catalyst. (f) EPR spectra of active species formed during the methane oxidation in 1 h.

Table 1 Comparison of catalytic activity of methane to methanol under visible light irradiation (λ ≥ 420 nm) with different oxidants external added. Note that PMS is an oxidant potassium persulfate.

Catalyst	Oxidants	Products (μmol g_cat.^-1)			Yield of CH₃OH per C_H2O2 (mL g_cat^-1)	Selectivity of CH₃OH (%)	Ref.
Catalyst	Oxidants	CH₃OH	HCHO	CO₂	Yield of CH₃OH per C_H2O2 (mL g_cat^-1)	Selectivity of CH₃OH (%)	Ref.
Pd₁/TiO₂	H₂O₂ (adding 100 mmol L^-1)	175	10	0	1.8	94	[14]
Au/WO₃	H₂O₂ (adding 500 mmol L^-1)	77	10	0	0.2	89	[44]
Au/WO₃	PMS	0	5	0	—	0	[44]
Cu/PCN	N/A	24.5	0	0	—	18.8	[45]
Cu_0.029/WO₃	O₂	0	4979	166	—	0	[46]
In₂O₃	O₂	0	15.8	0	—	0	[47]
U-NH₂	H₂O₂ (in-situ formed 189 μmol L^-1)	78	0	0	412	-100	this work

Fig. 5. Molecular dynamics snapshots of O2 molecules in U (a) and U-NH2 (b) unit cells over time. Red regions indicate the O2 molecule density field, and blue regions indicate the Zr atom density field in 3D isosurfaces.

Scheme 2. Schematic illustration of in-situ synthesis of H2O2 and partial oxidation of methane to methanol over U-NH2.

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