Optimizing reaction paths for methanol synthesis from CO<sub>2</sub> hydrogenation via metal-ligand cooperativity.
basic_science · Level V
Where this comes from
- Record sourced from PubMed, PMID 31015457.
- Also identified by DOI 10.1038/s41467-019-09918-z and PMC identifier 6478740.
- Licence recorded as CC BY.
- The licence permits redistribution, so the abstract is shown in full and the full text is available from the publisher.
Abstract
As diversified reaction paths exist over practical catalysts towards CO<sub>2</sub> hydrogenation, it is highly desiderated to precisely control the reaction path for developing efficient catalysts. Herein, we report that the ensemble of Pt single atoms coordinated with oxygen atoms in MIL-101 (Pt<sub>1</sub>@MIL) induces distinct reaction path to improve selective hydrogenation of CO<sub>2</sub> into methanol. Pt<sub>1</sub>@MIL achieves the turnover frequency number of 117 h<sup>-1</sup> in DMF under 32 bar at 150 °C, which is 5.6 times that of Pt<sub>n</sub>@MIL. Moreover, the selectivity for methanol is 90.3% over Pt<sub>1</sub>@MIL, much higher than that (13.3%) over Pt<sub>n</sub>@MIL with CO as the major product. According to mechanistic studies, CO<sub>2</sub> is hydrogenated into HCOO* as the intermediate for Pt<sub>1</sub>@MIL, whereas COOH* serves as the intermediate for Pt<sub>n</sub>@MIL. The unique reaction path over Pt<sub>1</sub>@MIL not only lowers the activation energy for the enhanced catalytic activity, but also contributes to the high selectivity for methanol.