In situ growth of embedded Pt nanoparticles in MIL-68(In)-derived In₂O₃ for enhanced CO₂ hydrogenation to methanol

Abstract

The catalytic conversion of CO₂ into methanol represents a promising route for reducing anthropogenic carbon emissions. Although Pt/In₂O₃ is an effective catalyst for this reaction, it suffers from severe sintering of both the Pt nanoparticles and the In₂O₃ support at high temperatures, leading to particle growth and deactivation. Herein, we report an in situ growth and embedding strategy using MIL-68(In) nanorods as a precursor to confine Pt nanoparticles within the derived In₂O₃ matrix. The resulting Pt/In₂O₃ catalyst exhibits ultrasmall In₂O₃ crystallites (11.8 nm) and a high surface area (48.3 m²∙g⁻¹). Comprehensive spectroscopic and microscopic analyses reveal strong Pt-O-In electronic interactions, which generate a high density of surface oxygen vacancies (41%) while minimizing the number of exposed Pt sites. These structural and electronic features synergistically enhance CO₂ activation and H₂ dissociation, reducing the apparent activation energy required for methanol formation to 62.2 kJ∙mol⁻¹. Under industrially relevant conditions (3 MPa, 300 °C, 12000 mL∙g_cat⁻¹∙h⁻¹), the optimized catalyst achieves a CO₂ conversion of 10.6% and a methanol production rate of 0.22 g_MeOH∙g_cat⁻¹∙h⁻¹, with exceptional stability over 180 h, outperforming previously reported Pt/In₂O₃ catalysts. This study offers a versatile metal-organic framework-mediated confinement strategy for designing durable high-performance metal/oxide catalysts for CO₂ hydrogenation.

Graphical abstract

Keywords

embedded Pt / in situ growth / CO₂ hydrogenation / Pt/In₂O₃ / methanol

References

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