Bifunctional hydroformylation on heterogeneous Rh-WOx pair site catalysts

Insoo Ro, Ji Qi, Seungyeon Lee, Mingjie Xu, Xingxu Yan, Zhenhua Xie, Gregory Zakem, Austin Morales, Jingguang G. Chen, Xiaoqing Pan, Dionisios G. Vlachos, Stavros Caratzoulas and Phillip Christopher ()
Additional contact information
Insoo Ro: University of California, Santa Barbara
Ji Qi: University of California, Santa Barbara
Seungyeon Lee: Catalysis Center for Energy Innovation
Mingjie Xu: University of California Irvine
Xingxu Yan: University of California Irvine
Zhenhua Xie: Brookhaven National Laboratory
Gregory Zakem: University of California, Santa Barbara
Austin Morales: University of California, Santa Barbara
Jingguang G. Chen: Brookhaven National Laboratory
Xiaoqing Pan: University of California Irvine
Dionisios G. Vlachos: Catalysis Center for Energy Innovation
Stavros Caratzoulas: University of Delaware
Phillip Christopher: University of California, Santa Barbara

Nature, 2022, vol. 609, issue 7926, 287-292

Abstract: Abstract Metal-catalysed reactions are often hypothesized to proceed on bifunctional active sites, whereby colocalized reactive species facilitate distinct elementary steps in a catalytic cycle1–8. Bifunctional active sites have been established on homogeneous binuclear organometallic catalysts9–11. Empirical evidence exists for bifunctional active sites on supported metal catalysts, for example, at metal–oxide support interfaces2,6,7,12. However, elucidating bifunctional reaction mechanisms on supported metal catalysts is challenging due to the distribution of potential active-site structures, their dynamic reconstruction and required non-mean-field kinetic descriptions7,12,13. We overcome these limitations by synthesizing supported, atomically dispersed rhodium–tungsten oxide (Rh-WOx) pair site catalysts. The relative simplicity of the pair site structure and sufficient description by mean-field modelling enable correlation of the experimental kinetics with first principles-based microkinetic simulations. The Rh-WOx pair sites catalyse ethylene hydroformylation through a bifunctional mechanism involving Rh-assisted WOx reduction, transfer of ethylene from WOx to Rh and H2 dissociation at the Rh-WOx interface. The pair sites exhibited >95% selectivity at a product formation rate of 0.1 gpropanal cm−3 h−1 in gas-phase ethylene hydroformylation. Our results demonstrate that oxide-supported pair sites can enable bifunctional reaction mechanisms with high activity and selectivity for reactions that are performed in industry using homogeneous catalysts.

Date: 2022
References: Add references at CitEc
Citations: View citations in EconPapers (7)

Downloads: (external link)
https://www.nature.com/articles/s41586-022-05075-4 Abstract (text/html)
Access to the full text of the articles in this series is restricted.

Related works:
This item may be available elsewhere in EconPapers: Search for items with the same title.

Export reference: BibTeX RIS (EndNote, ProCite, RefMan) HTML/Text

Persistent link: https://EconPapers.repec.org/RePEc:nat:nature:v:609:y:2022:i:7926:d:10.1038_s41586-022-05075-4

Ordering information: This journal article can be ordered from
https://www.nature.com/

DOI: 10.1038/s41586-022-05075-4

Access Statistics for this article

Nature is currently edited by Magdalena Skipper

More articles in Nature from Nature
Bibliographic data for series maintained by Sonal Shukla () and Springer Nature Abstracting and Indexing ().