New catalysts based on non-crystalline metals

This thesis explores the catalytic potential of metallic glasses (MGs) and their combination with cerium oxide (CeO2) for low-temperature carbon monoxide (CO) oxidation and CO preferential oxidation (COPrOx) reactions. Metallic glasses, due to their non-crystalline structure and tunable composition, offer a promising platform for catalytic applications when appropriately engineered. The study focuses on three primary MG systems: Ce65Al35, Pd77Si16.5Cu6.5, and Cu48Zr48Al4, examining their structural characteristics, and catalytic behavior. The results showed that the Ce65Al35 metallic glass has limited catalytic activity, even after various activation treatments such as ball milling, calcination, or combination with CeO2. However, doping the binary Ce-Al system with Pd (Ce61Al35Pd4) markedly improved performance, achieving 100% CO conversion at 300 °C when ball milled.
 
Interestingly, mixing this ternary MG with CeO2 did not provide further enhancement, indicating that Pd’s role is dominant and not synergistic with ceria. The Pd77Si16.5Cu6.5 MG emerged as the most effective standalone catalyst, delivering full CO conversion at only 240 °C. Which could be attributed to Pd and its optimized distribution in the amorphous matrix. Control experiments with binary alloys (Pd77Si23 and Cu6Si94) highlighted the importance of both composition and structural processing, particularly the necessity of melt spinning and ball milling to generate active, fine-particle structures.

Another major contribution of this work is the development and detailed characterization of Cu-based MG/CeO2 composites, especially Cu48Zr48Al4.These systems showed strong activity and stability in both CO and COPrOx reactions, with performance enhanced through ball milling. Structural and operando analyses (XPS, EXAFS, NEXAFS, and XRD) confirmed that the catalysts undergo surface rearrangement during reaction, stabilizing catalytically active Cu(I) atoms. A spontaneous aging phenomenon and a similar change under hydrogen pre-reduction pointed to the dynamic evolution of active sites during real operation conditions. This study demonstrates that mechanochemical synthesis and careful structural design of MG/CeO2 composites enable the development of efficient, low-cost, and stable oxidation catalysts. These findings offer new strategies for creating highly active materials for pollution control and hydrogen purification technologies, opening the path to use amorphous metals for heterogeneous catalysis.