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Pretreatment-programmed interfacial Ni reconstruction controls CO2 hydrogenation selectivity over a CeO2-modified Cu catalyst promoted with dilute Ni
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DOI：10.1016/j.colsurfa.2026.140676.png)
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Abstract
En 中文
Hydrogen pretreatment can reconfigure dilute promoters at metal–oxide boundaries and thereby alter catalytic selectivity. Here we show that the H2 pretreatment temperature controls CO2 hydrogenation on a CeO2-modified Cu catalyst promoted with dilute Ni (nominal Ni/Cu = 1:9, denoted CeNiCu). After reduction at 600 °C, the catalyst exhibits RWGS-dominated behavior with near-unity CO selectivity and stable operation, whereas reduction at 400 °C leads to appreciable CH4 formation under identical conditions (0.1 MPa, CO2/H2 = 1/4). Quantitative H2-TPR analysis confirms that bulk reduction is essentially complete by 400 °C, ruling out incomplete reduction as the origin of the selectivity difference. STEM-EDS, operando SR-XRD-MS, and quasi-in situ Ni K-edge XAFS show that increasing the pretreatment temperature redistributes dilute Ni from the Cu–CeO2 perimeter into a Cu-rich Ni–Cu mixed phase. APXPS, Ce L3-edge XANES, and Raman spectroscopy further indicate that the 400 °C-pretreated catalyst retains interfacial Ni–O species adjacent to a more defect-rich, relatively Ce3+-enriched ceria perimeter, whereas the 600 °C-pretreated catalyst contains predominantly metallic, electronically enriched Ni in a Cu-rich environment next to less defective ceria. CO2-TPD, CO-TPD, H2 chemisorption, in situ DRIFTS, and simplified DFT calculations collectively show that this reconstruction changes the post-RWGS fate of CO from further hydrogenation to desorption. These results identify pretreatment-programmed interfacial Ni reconstruction as a practical handle for suppressing methanation and stabilizing RWGS selectivity.
Keywords:
CO2 hydrogenation
Ni reconstruction
CeO2-modified Cu catalyst
RWGS selectivity
pretreatment temperature
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