Interlayer engineering of molybdenum disulfide toward efficient electrocatalytic hydrogenation

Jingwen Tan; Wenbiao Zhang; Yijin Shu; Haiyang Lu; Yi Tang; Qingsheng Gao

doi:10.1016/j.scib.2020.11.002

Interlayer engineering of molybdenum disulfide toward efficient electrocatalytic hydrogenation

Sci Bull (Beijing). 2021 May 30;66(10):1003-1012. doi: 10.1016/j.scib.2020.11.002. Epub 2020 Nov 9.

Authors

Jingwen Tan¹, Wenbiao Zhang¹, Yijin Shu¹, Haiyang Lu², Yi Tang², Qingsheng Gao³

Affiliations

¹ College of Chemistry and Materials Science, Guangdong Provincial Key Laboratory of Functional Supramolecular Coordination Materials and Applications, Jinan University, Guangzhou 510632, China.
² Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Laboratory of Advanced Materials and Collaborative Innovation Center of Chemistry for Energy Materials (iCHEM), Fudan University, Shanghai 200433, China.
³ College of Chemistry and Materials Science, Guangdong Provincial Key Laboratory of Functional Supramolecular Coordination Materials and Applications, Jinan University, Guangzhou 510632, China. Electronic address: tqsgao@jnu.edu.cn.

PMID: 36654245
DOI: 10.1016/j.scib.2020.11.002

Abstract

Electrocatalytic hydrogenation (ECH) enables the sustainable production of chemicals under ambient condition; however, suffers from serious competition with hydrogen (H₂) evolution and the use of precious metals as electrocatalysts. Herein, molybdenum disulfide is for the first time developed as an efficient and noble-metal-free catalyst for ECH via in situ intercalation of ammonia or alkyl-amine cations. This interlayer engineering regulates phase transition (2H → 1 T), and effectively ameliorates electronic configurations and surface hydrophobicity to promote the ECH of biomass-derived oxygenates, while prohibiting H₂ evolution. The optimal one intercalated by dimethylamine (MoS₂-DMA) is capable of hydrogenating furfural (FAL) to furfuryl alcohol with high Faradaic efficiency of 86.3%-73.3% and outstanding selectivity of >95.0% at -0.25 to -0.65 V (vs. RHE), outperforming MoS₂ and other conventional metals. Such prominent performance stems from the enhanced chemisorption and surface hydrophobicity. The chemisorption of H intermediate and FAL, synchronously strengthened on the edge-sites of MoS₂-DMA, accelerates the surface elementary step following Langmuir-Hinshelwood mechanism. Moreover, the improved hydrophobicity benefits FAL affinity to overcome diffusion limitation. Discovering the effective modulation of MoS₂ from a typical H₂ evolution electrocatalyst to a promising candidate for ECH, this study broadens the scope to exploit catalysts used for electrochemical synthesis.

Keywords: Binding energy; Electrocatalytic hydrogenation; Interlayer engineering; Molybdenum disulfide; Surface hydrophobicity.