Selective coordination activation regulating the selectivity for photocatalytic hydrogenation of α, β-unsaturated aldehyde over Pd/MIL-100(FeaCub)

• Published in: Applied catalysis. B, Environmental Environmental, 2024-01, Vol.340, p.123162, Article 123162
• Main Authors: Wang, Zhiwen, Kang, Yueyue, Shi, Yingzhang, Liu, Cheng, Liu, Yunni, Lin, Jun, Bi, Jinhong, Wu, Ling
• Format: Article
• Language: English
• Subjects: Coordination activation; Hydrogenation; MIL-100(Fe/Cu); Photocatalyst; β-Unsaturated aldehydes
• ISSN: 0926-3373; 1873-3883
• DOI: 10.1016/j.apcatb.2023.123162

Here, the mixed metal nodes MOFs, Pd/MIL-100(FeaCub), were constructed as photocatalysts for hydrogenation of α, β-unsaturated aldehyde (UAL) under visible light. 1 wt% Pd/MIL-100(Fe0.81Cu0.19) can convert a range of UAL to saturated aldehydes (SAL) with a high efficiency (≈ 100 %) and selectivity (≈ 98 %). The results of XPS and in situ DRIFTS reveal that UAL can be selectively activated via a coordination of -CC- on Cu2+ sites, determining the high selectivity of the photocatalytic reaction. The mixed metal nodes and Pd clusters can improve the transformation and separation of photogenerated electrons-holes. EPR result suggests that photogenerated carriers can facilitate the generation of H·on Pd/MIL-100(Fe0.81Cu0.19), enhancing the catalytic activity. A possible mechanism is proposed for elucidating the catalytic processes at the molecular level. This work provides a valuable strategy for tailoring the selectivity of photocatalytic hydrogenation via selective coordination activation. [Display omitted] •Functionalized Pd/MIL-100(Fe0.81Cu0.19) was successfully constructed.•High cinnamaldehyde conversion (100 %) and saturated aldehydes selectivity (98 %) were obtained.•The coordination of -CC- on Cu2+ sites determines the selectivity.•The mechanism of the selective α, β-unsaturated aldehyde hydrogenation is revealed.