Solar-Driven Reforming of Methane and Nitrogen to Methanol and Ammonium on Iron-Modified Zeolite under Ambient Conditions in Water

Mei Ren; Jun Li; Manhong Huang; Donghui Chen; Xiaoliang Li; Xiaoliang Yan; Qi An; Songmei Sun

doi:10.1021/acs.inorgchem.3c02393

Solar-Driven Reforming of Methane and Nitrogen to Methanol and Ammonium on Iron-Modified Zeolite under Ambient Conditions in Water

Inorg Chem. 2023 Sep 11;62(36):14804-14814. doi: 10.1021/acs.inorgchem.3c02393. Epub 2023 Aug 29.

Authors

Mei Ren¹, Jun Li², Manhong Huang^{1

3}, Donghui Chen¹, Xiaoliang Li⁴, Xiaoliang Yan⁴, Qi An², Songmei Sun^{1

3}

Affiliations

¹ Textile Pollution Controlling Engineering Center of Ministry of Environmental Protection, College of Environmental Science and Engineering, Donghua University, Shanghai 201620, China.
² Department of Materials Science and Engineering, Iowa State University, Ames, Iowa 50011, United States.
³ Shanghai Institute of Pollution Control and Ecological Security, 1239 Siping Road, Shanghai 200092, China.
⁴ State Key Laboratory of Clean and Efficient Coal Utilization, Taiyuan University of Technology, Taiyuan 030024, China.

PMID: 37644618
DOI: 10.1021/acs.inorgchem.3c02393

Abstract

Artificial photosynthesis from selective methane oxidation or nitrogen reduction to value-added chemicals provides a promising pathway for the sustainable chemical industry, while still remaining a great challenge due to the extreme difficulty in C-H and N≡N bond cleavage under ambient conditions. Catalysts that can cocatalyze these two reactions simultaneously are rarely reported. Here, Fe-ZSM-5 with highly dispersed extra-framework Fe-oxo species enables efficient and selective photocatalytic conversion of methane and nitrogen to coproduce methanol and ammonia using H₂O as the redox reagent under ambient conditions. The optimized Fe-ZSM-5 photocatalyst achieves up to 0.88 mol/mol_Fe·h of methanol products with 97% selectivity. Meanwhile, the productivity of ammonia is 0.61 mol/mol_Fe·h. In situ EPR and DRIFT studies disclose that water serves as a redox reagent to provide hydroxyl radicals for methane oxidation and protons for nitrogen hydrogenation. Quantum chemical calculations revealed that Fe-oxo species play a significant role in the coactivation of methane and nitrogen molecules, which lowers the energy barriers of rate-determining steps for methanol and ammonia generation.