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

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/CO 2 emissions. However, the unsupported metal oxide catalysts (such as α-Fe 2 O 3 ) 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-Fe 2 O 3 nanoparticles (NPs). Systematic characterization of the obtained materials through analytical techniques demonstrated that mesoporous nanostructured unsupported α-Fe 2 O 3 with abundant oxygen vacancies (OV-rich α-Fe 2 O 3 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-Fe 2 O 3 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 H 2 g -1 min -1 ) after 480 min. This outstanding thermocatalytic performance of OV-rich α-Fe 2 O 3 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 CH 4 decomposition into hydrogen fuel and carbon nanomaterials.