Scalable one-step preparation of supported ultrasmall CeO2 with optimized Lewis acid strength for efficient dimethyl carbonate synthesis using 2‑cyanopyridine
Journal
Applied Catalysis B: Environment and Energy
Journal Volume
398
Start Page
126992
ISSN
0926-3373
Date Issued
2026-12-05
Author(s)
Xiao, Zhanping
Xu, Ruolei
Liao, Yin-Song
Tian, Linyuan
Yuan, Bo
Cui, Yifan
Liu, Guoliang
Chou, Pi-Tai
Peng, Yung-Kang
Abstract
The green synthesis of dimethyl carbonate (DMC) from CO2 and methanol using CeO2-based catalysts, particularly with 2-cyanopyridine (2-Cp) as dehydrant, has attracted considerable attention over the past decade. However, preparing high-performance catalysts often requires multiple steps and labor-intensive purifications, even for pristine CeO2. These drawbacks, together with unclear catalytic correlations resulting from the limited resolution of traditional surface techniques, hinder practical application. To address these issues, we developed a simple, scalable method to synthesize ultrasmall CeO2 nanoparticles (<5 nm) densely supported within a carbon framework that prevents aggregation. The resulting catalyst is ready-to-use without purification, offering a feasible route to large-scale production. Using advanced probe-assisted nuclear magnetic resonance (NMR), we reveal that Lewis acid strength at Ce sites varies substantially with CeO2 particle size and heteroatom coordination, which affects differently to methanol and 2-Cp activation in DMC synthesis and 2-Cp hydration. The latter reaction is particularly sensitive and may thus proceed via an unconventional pathway. By contrast, traditional surface techniques fail to resolve these distinctions. The optimized catalyst displays high DMC activity and recyclability, outperforming its unsupported counterparts. Overall, our findings guide mass production of highly-active ultrasmall CeO2 catalysts and provide a practical foundation for implementing DMC synthesis with 2-Cp.
Subjects
CeO2
Dimethyl carbonate synthesis
Facile and scalable
Lewis acidic strength
Probe-assisted NMR
Publisher
Elsevier BV
Type
journal article