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Electrochemical semi\u2010hydrogenation presents a sustainable alternative to the traditional thermal process. In this research, affordable copper acetylacetonate is employed as a catalyst precursor for the electrocatalytic hydrogenation of alkynes, using MeOH as the hydrogen source in an undivided cell. Good to excellent yields for both aromatic and aliphatic internal\/terminal alkynes are obtained under constant current conditions. Notably, up to 99% Z selectivity is achieved for various internal alkynes. Mechanistic investigations revealed the formation of copper nanoparticles (NPs) at the cathode during electrolysis, acting as the catalyst for the selective semireduction of alkynes. The copper NPs deposited cathode demonstrated reusable for further hydrogenation.<\/jats:p>","DOI":"10.1002\/smll.202401107","type":"journal-article","created":{"date-parts":[[2024,3,26]],"date-time":"2024-03-26T13:20:50Z","timestamp":1711459250000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":3,"title":["Membrane\u2010Free Selective Semi\u2010Hydrogenation of Alkynes Over an In Situ Formed Copper Nanoparticle Electrode"],"prefix":"10.1002","volume":"20","author":[{"given":"Pengyu","family":"Guo","sequence":"first","affiliation":[{"name":"School of Chemistry and Material Sciences Hangzhou Institute of Advanced Study University of Chinese Academy of Sciences  1 Sub\u2010lane Xiangshan Hangzhou 310024 China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Yousen","family":"Xu","sequence":"additional","affiliation":[{"name":"School of Chemistry and Material Sciences Hangzhou Institute of Advanced Study University of Chinese Academy of Sciences  1 Sub\u2010lane Xiangshan Hangzhou 310024 China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Hao","family":"Wu","sequence":"additional","affiliation":[{"name":"School of Chemistry and Material Sciences Hangzhou Institute of Advanced Study University of Chinese Academy of Sciences  1 Sub\u2010lane Xiangshan Hangzhou 310024 China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1736-1633","authenticated-orcid":false,"given":"Lei","family":"Zhang","sequence":"additional","affiliation":[{"name":"School of Chemistry and Material Sciences Hangzhou Institute of Advanced Study University of Chinese Academy of Sciences  1 Sub\u2010lane Xiangshan Hangzhou 310024 China"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2024,3,26]]},"reference":[{"key":"e_1_2_7_1_1","doi-asserted-by":"publisher","DOI":"10.1126\/science.1156660"},{"key":"e_1_2_7_1_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr3001753"},{"key":"e_1_2_7_1_3","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.9b00230"},{"key":"e_1_2_7_2_1","doi-asserted-by":"publisher","DOI":"10.1038\/ncomms6787"},{"key":"e_1_2_7_2_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.6b10817"},{"key":"e_1_2_7_2_3","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.7b02915"},{"key":"e_1_2_7_2_4","doi-asserted-by":"publisher","DOI":"10.1038\/s41467-018-05052-4"},{"key":"e_1_2_7_2_5","doi-asserted-by":"publisher","DOI":"10.1021\/acs.iecr.8b03627"},{"key":"e_1_2_7_2_6","doi-asserted-by":"publisher","DOI":"10.1016\/j.chempr.2018.02.011"},{"key":"e_1_2_7_2_7","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.7b01471"},{"key":"e_1_2_7_3_1","doi-asserted-by":"publisher","DOI":"10.1038\/nchem.1693"},{"key":"e_1_2_7_3_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.9b09856"},{"key":"e_1_2_7_4_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja01245a055"},{"key":"e_1_2_7_4_2","doi-asserted-by":"publisher","DOI":"10.1149\/1.2407974"},{"key":"e_1_2_7_4_3","first-page":"787","volume":"69","author":"Byrne M.","year":"1973","journal-title":"J. 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