Scalable Synthesis of Oxygen Vacancy-Rich Unsupported Iron Oxide for Efficient Thermocatalytic Conversion of Methane to Hydrogen and Carbon Nanomaterials

Abdulrahman I Alharthi; Talal F Qahtan; Maged N Shaddad; Mshari A Alotaibi; Satam Alotibi; Amani M Alansi

doi:10.3390/nano13172461

Scalable Synthesis of Oxygen Vacancy-Rich Unsupported Iron Oxide for Efficient Thermocatalytic Conversion of Methane to Hydrogen and Carbon Nanomaterials

Nanomaterials (Basel). 2023 Aug 31;13(17):2461. doi: 10.3390/nano13172461.

Authors

Abdulrahman I Alharthi¹, Talal F Qahtan², Maged N Shaddad¹, Mshari A Alotaibi¹, Satam Alotibi², Amani M Alansi³

Affiliations

¹ Chemistry Department, College of Science and Humanities in Al-Kharj, Prince Sattam Bin Abdulaziz University, P.O. Box 83, Al-Kharj 11942, Saudi Arabia.
² Physics Department, College of Science and Humanities in Al-Kharj, Prince Sattam Bin Abdulaziz University, P.O. Box 83, Al-Kharj 11942, Saudi Arabia.
³ Chemistry Department, King Saud University, Riyadh 12372, Saudi Arabia.

Abstract

Thermocatalytic methane decomposition (TCMD) involving metal oxides is a more environmentally friendly and cost-effective strategy for scalable hydrogen fuel production compared to traditional methane steam reforming (MSR), as it requires less energy and produces fewer CO/CO₂ emissions. However, the unsupported metal oxide catalysts (such as α-Fe₂O₃) that would be suited for this purpose exhibit poor performance in TCMD. To overcome this issue, a novel strategy was developed as a part of this work, whereby oxygen vacancies (OVs) were introduced into unsupported α-Fe₂O₃ nanoparticles (NPs). Systematic characterization of the obtained materials through analytical techniques demonstrated that mesoporous nanostructured unsupported α-Fe₂O₃ with abundant oxygen vacancies (OV-rich α-Fe₂O₃ NPs) could be obtained by direct thermal decomposition of ferric nitrate at different calcination temperatures (500, 700, 900, and 1100 °C) under ambient conditions. The thermocatalytic activity of the resulting OV-rich α-Fe₂O₃ NPs was assessed by evaluating the methane conversion, hydrogen formation rate, and amount of carbon deposited. The TCMD results revealed that 900 °C was the most optimal calcination temperature, as it led to the highest methane conversion (22.5%) and hydrogen formation rate (47.0 × 10^-5 mol H₂ g^-1 min^-1) after 480 min. This outstanding thermocatalytic performance of OV-rich α-Fe₂O₃ NPs is attributed to the presence of abundant OVs on their surfaces, thus providing effective active sites for methane decomposition. Moreover, the proposed strategy can be cost-effectively scaled up for industrial applications, whereby unsupported metal oxide NPs can be employed for energy-efficient thermocatalytic CH₄ decomposition into hydrogen fuel and carbon nanomaterials.

Keywords: calcination process; carbon nanomaterials; hydrogen formation; methane decomposition; oxygen vacancies; unsupported α-Fe2O3 nanoparticles.

Grants and funding

The authors extend their appreciation to the Deputyship for Research& Innovation, Ministry of Education in Saudi Arabia for funding this research work through the project number (2022/01/22126).