Alloying promotion of Pd-based metallenes in electrocatalytic hydrogenation of functionalized nitroarenes. Issue 14 (24th March 2023)

• Record Type: Journal Article
• Authors: Zhang, Wenbiao; Zhang, Wanling; Tan, Jingwen; Pan, Di; Tang, Yi; Gao, Qingsheng
• Is Part Of: Journal of materials chemistry. Volume 11:Issue 14(2023)
• Page Start: 7505
• Page End: 7512
• Publication Date: 2023-03-24
• Subjects: Materials -- Research -- Periodicals; Chemistry, Analytic -- Periodicals; Environmental sciences -- Research -- Periodicals; 543.0284
• DOI: 10.1039/d2ta10021e
• Languages: English
• ISSNs: 2050-7488

Abstract

Abstract : Pd–M (M = Cr, Mo, and W) metallenes are for the first time introduced as efficient electrocatalysts for the ECH of nitroarenes, in which the alloying promotion can be intrinsically ascribed to the boosted chemisorption/activation of a nitro group. Abstract : Electrocatalytic hydrogenation (ECH) provides a controllable and sustainable reduction of organic compounds via multi-electron-transfer processes under ambient conditions, which urgently demands high-performance electrocatalysts with satisfactory activity and selectivity. Here, two-dimensional Pd-based metallenes are for the first time introduced as efficient electrocatalysts for the ECH of nitroarenes, showing the intrinsic promotion of active sites by alloying effects. Thereinto, a Pd–Mo metallene with a highly exposed active surface and strong electronic interactions between Pd and Mo atoms affords the chemoselective hydrogenation of 4-nitrostyrene (4-NS) toward value-added 4-vinylaniline (4-VA). At −0.25 V vs. RHE, it reaches a high selectivity (>90.0%) and faradaic efficiency (78.3%) of 4-VA, outperforming the counterparts of a home-made Pd metallene and commercial Pd/C. The consistent alloying promotion is further verified on a series of Pd–M (M = Cr, Mo, and W) metallenes, with the specific activity sequence (Pd–Mo > Pd–W > Pd–Cr > Pd) that can be theoretically interpreted by the gradually strengthened chemisorption of 4-NS after alloying Pd with M. Moreover, the good efficiency within a broad substrate scope highlights the promise of Pd-based metallenes in electrochemical refinery.