Unveiling subsurface hydrogen inhibition for promoting electrochemical transfer semihydrogenation of alkynes with water

doi:10.1016/S1872-2067(22)64145-7

Abstract

Abstract:

Highly selective electrocatalytic semihydrogenation of alkynes to alkenes with water as the hydrogen source over palladium-based electrocatalysts is significant but remains a great challenge because of the excessive hydrogenation capacity of palladium. Here, we propose that an ideal palladium catalyst should possess weak alkene adsorption and inhibit subsurface hydrogen formation to stimulate the high selectivity of alkyne semihydrogenation. Therefore, sulfur-modified Pd nanowires (Pd-S NWs) are designedly prepared by a solid-solution interface sulfuration method with KSCN as the sulfur source. The introduction of S weakens the alkene adsorption and prevents the diffusion of active hydrogen (H*) into the Pd lattice to form unfavorable subsurface H*. As a result, electrocatalytic alkyne semihydrogenation is achieved over a Pd-S NWs cathode with wide substrate scopes, potential-independent up to 99% alkene selectivity, good fragile groups compatibility, and easily synthesized deuterated alkenes. An adsorbed hydrogen addition mechanism of this semihydrogenation reaction is proposed. Importantly, an easy modification of commercial Pd/C by in situ addition of SCN^- enabling the gram-scale synthesis of an alkene with 99% selectivity and 95% conversion highlights the promising potential of our method.

Key words: Electrocatalysis, Alkyne semihydrogenation, Selectivity, Hydrogen adsorption, Interface sulfuration

Qi Hao, Yongmeng Wu, Cuibo Liu, Yanmei Shi, Bin Zhang. Unveiling subsurface hydrogen inhibition for promoting electrochemical transfer semihydrogenation of alkynes with water[J]. Chinese Journal of Catalysis, 2022, 43(12): 3095-3100.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(22)64145-7

https://www.cjcatal.com/EN/Y2022/V43/I12/3095

Figures/Tables 5

Fig. 1. (a) TEM, HRTEM, and EDS elemental mapping images of Pd-S NWs. (b) XRD patterns of Pd-S NWs and Pd NWs. XPS spectra of S 2p (c) and Pd 3d (d) of Pd-S NWs.

Fig. 2. Potential-dependent 1a conversion 2a selectivity and 2a FE over Pd-S NWs (a) and Pd NWs (b). Time-dependent (c) and cycle-dependent (d) 1a Conversion and 2a Selectivity over PdS NWs.

Fig. 3. (a) CV curves of Pd NWs and Pd-S NWs in 0.5 mol/L Na2SO4. (b) Electrochemical in situ XRD pattern performed in 1.0 mol/L KOH. (c) Chronoamperometry measurements recorded for Pd NWs and Pd-S NWs at a reductive potential (absorption) and oxidative potential (desorption). (d) Calculated amounts of transformed charge of Pd NWs and Pd-S NWs from chronoamperometry measurements. Inset: quantification of hydrogen absorption in Pd NWs and Pd-S NWs during chronoamperometry measurements.

Table 1 Substrate scopes for electrocatalytic transfer semihydrogenation and semideuterization of alkynes with H2O over a Pd-S cathode.

Fig. 4. (a) Scheme of electrocatalytic gram-scale semihydrogenation over commercial Pd/C with SCN- addition. (b) 1a Conversion and 2a Selectivity over commercial Pd/C with and without SCN- addition. (c) Time-dependent 1a Conversion and 2a Selectivity during gram-scale semihydronation over commercial Pd/C with SCN- addition.

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