Effect of Coordination Environment Surrounding a Single Pt Site on the Liquid-Phase Aerobic Oxidation of 5-Hydroxymethylfurfural
| Autor: | Tiansheng Deng, Guangqiang Lv, Yu Meng, Hongliang Wang, Chaoxin Yang, Jun Zhao, Wanzhen Zhu, Yingxiong Wang, Xianglin Hou, Wei Hu |
|---|---|
| Rok vydání: | 2021 |
| Předmět: | |
| Zdroj: | ACS Applied Materials & Interfaces. 13:48582-48594 |
| ISSN: | 1944-8252 1944-8244 |
| Popis: | As the frontier in heterogeneous catalyst, a monomer and positively charged active sites in the single-atom catalyst (SAC), anchored by high electronegative N, O, S, P, etc., atoms, may not be active for the multispecies (O2, substrates, intermediates, solvent etc.) involved liquid-phase aerobic oxidation. Here, with catalytic, aerobic oxidation of 5-hydroxymethylfurfural as an example, Pt SAC (Pt1-N4) was synthesized and tested first. With commercial Pt/C (Pt loading of 5 wt %) as a benchmark, 2,5-furandicarboxylic acid (FDCA) yield of 97.6% was obtained. Pt SAC (0.56 wt %) gave a much lower FDCA yield (28.8%). By changing the coordination atoms from highly electronegative N to low electronegative Co atoms, the prepared Pt single-atom alloy (SAA, Pt1-Co3) catalyst with ultralow Pt loading (0.06 wt %) gave a much high FDCA yield (99.6%). Density functional theory (DFT) calculations indicated that positively charged Pt sites (+0.712e) in Pt1-N4 almost lost the capability for oxygen adsorption and activation, as well as the adsorption for the key intermediate. In Pt1-Co3 SAA, the central negatively charged Pt atom (-0.446e) facilitated the adsorption of the key intermediate; meanwhile, the nearby Co atoms around the Pt atom constituted the O2-preferred adsorption/activation sites. This work shows the difference between the SAC with NPs and the SAA during liquid-phase oxidation of HMF and gives a useful guide in the future single-atom catalyst design in other related reactions. |
| Databáze: | OpenAIRE |
| Externí odkaz: |
|