Wang, Weiyu, Lu, Bintian, Lewis, Richard J., Chu, Yueying, Wang, Qiang, Hutchings, Graham J.  ORCID: https://orcid.org/0000-0001-8885-1560, Xu, Jun and Deng, Feng
2026.
Dynamic mechanism switching in butene isomerization on PdAu nanocatalysts revealed by parahydrogen-induced polarization nuclear magnetic resonance spectroscopy.
ACS Catalysis
16
(12)
, pp. 11442-11455.
10.1021/acscatal.6c02116
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Abstract
The selective hydrogenation of 1,3-butadiene to 1-butene represents a pivotal process in the purification of industrial olefin streams, yet its performance is often hindered by undesired 1-butene isomerization to 2-butene. Herein, we employ parahydrogen-induced polarization (PHIP) nuclear magnetic resonance (NMR) spectroscopy as a pathway-sensitive probe to unravel the mechanistic origin of this isomerization. Pd−Au alloy nanoparticles supported on TiO2 with systematically tuned Pd/Au mass fractions reveal a distinct mechanistic transition governing 1-butene reactivity. Combined PHIP NMR, CO diffuse reflectance infrared Fourier transform spectroscopy (CO-DRIFTS), and quasi-in situ X-ray photoelectron spectroscopy (XPS) analyses demonstrate that on contiguous Pd ensembles, 1-butene isomerization is primarily driven by hydrogen surface coverage. Progressive incorporation of Au into the alloy disrupts these Pd ensembles, generating isolated Pd sites that shift the reaction control toward a competitive adsorption regime, wherein preferential 1,3-butadiene adsorption effectively suppresses 1-butene isomerization. Under reaction conditions, carbonaceous restructuring further stabilizes the single-atom Pd species, reinforcing the inhibition of isomerization.
| Item Type: | Article |
|---|---|
| Date Type: | Publication |
| Status: | Published |
| Schools: | Schools > Chemistry Research Institutes & Centres > Cardiff Catalysis Institute (CCI) |
| Uncontrolled Keywords: | RRS applied - AB 03/07/2026 |
| Publisher: | American Chemical Society |
| ISSN: | 2155-5435 |
| Date of First Compliant Deposit: | 3 July 2026 |
| Date of Acceptance: | 12 May 2026 |
| Last Modified: | 02 Aug 2026 01:15 |
| URI: | https://orca.cardiff.ac.uk/id/eprint/187459 |
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