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.

电催化氢化 (ECH) 可在环境条件下实现化学品的可持续生产；然而，与氢气 (H ₂ ) 的析出和贵金属作为电催化剂的使用存在严重竞争。在此，二硫化钼通过原位插入氨或烷基胺阳离子，首次被开发为一种高效且无贵金属的ECH催化剂。这种层间工程调节相变 (2H → 1 T)，并有效改善电子构型和表面疏水性，以促进生物质衍生的含氧化合物的 ECH，同时阻止 H ₂演化。最佳的插层二甲胺（MoS ₂-DMA) 能够将糠醛 (FAL) 氢化为糠醇，具有 86.3%–73.3% 的高法拉第效率和在 -0.25 至 -0.65 V（相对于 RHE）下 >95.0% 的出色选择性，优于 MoS ₂和其他常规金属。这种突出的性能源于增强的化学吸附和表面疏水性。_{H 中间体和 FAL 的化学吸附在 MoS 2} -DMA的边缘位点上同步增强，按照 Langmuir-Hinshelwood 机制加速了表面基本步骤。此外，改进的疏水性有利于 FAL 亲和力克服扩散限制。从典型的 H ₂中发现 MoS _{2的有效调制}进化电催化剂到 ECH 的有前途的候选者，这项研究拓宽了开发用于电化学合成的催化剂的范围。