{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,4,30]],"date-time":"2026-04-30T18:18:17Z","timestamp":1777573097751,"version":"3.51.4"},"reference-count":37,"publisher":"MDPI AG","issue":"15","license":[{"start":{"date-parts":[[2025,7,23]],"date-time":"2025-07-23T00:00:00Z","timestamp":1753228800000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100003787","name":"Hebei Provincial Natural Science Foundation","doi-asserted-by":"publisher","award":["B2024108004"],"award-info":[{"award-number":["B2024108004"]}],"id":[{"id":"10.13039\/501100003787","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>In the field of green chemistry, the development of more sustainable and cost-efficient methods for synthesizing primary amines is of paramount importance, with catalyst research being central to this effort. This work presents a facile, aqueous-phase synthesis of highly active cobalt catalysts (Co-Ph@SiO2(x)) via pyrolysis of silica-supported cobalt\u2013phenanthroline complexes. The optimized Co-Ph@SiO2(900) catalyst achieved exceptional performance (&gt;99% conversion, &gt;98% selectivity) in the reductive amination of acetophenone to 1-phenylethanamine using NH3\/H2. Systematic studies revealed that its exceptional performance originates from the in situ pyrolysis of the cobalt\u2013phyllosilicate complex. This process promotes the uniform distribution of metal cobalt nanoparticles, simultaneously enhancing porosity and imparting bifunctional (acidic and basic) properties to the catalyst, resulting in outstanding catalytic activity and selectivity. The catalyst demonstrated broad applicability, efficiently converting diverse ketones (aryl-alkyl, dialkyl, bioactive) and aldehydes (halogenated, heterocyclic, biomass-derived) into primary amines with high yields (up to 99%) and chemoselectivity (&gt;40 examples). This sustainable, non-noble metal-based catalyst system offers significant potential for industrial primary amine synthesis and provides a versatile tool for developing highly selective and active heterogeneous catalysts.<\/jats:p>","DOI":"10.3390\/molecules30153089","type":"journal-article","created":{"date-parts":[[2025,7,23]],"date-time":"2025-07-23T14:22:44Z","timestamp":1753280564000},"page":"3089","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":1,"title":["Simple Cobalt Nanoparticle-Catalyzed Reductive Amination for Selective Synthesis of a Broad Range of Primary Amines"],"prefix":"10.3390","volume":"30","author":[{"given":"Bingxiao","family":"Zheng","sequence":"first","affiliation":[{"name":"Functional Polymer Materials R&D and Engineering Application Technology Innovation Center of Hebei Province, Xingtai University, Xingtai 054001, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Liqin","family":"Yang","sequence":"additional","affiliation":[{"name":"Functional Polymer Materials R&D and Engineering Application Technology Innovation Center of Hebei Province, Xingtai University, Xingtai 054001, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0009-0003-2059-3851","authenticated-orcid":false,"given":"Yashuang","family":"Hei","sequence":"additional","affiliation":[{"name":"Functional Polymer Materials R&D and Engineering Application Technology Innovation Center of Hebei Province, Xingtai University, Xingtai 054001, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7196-4833","authenticated-orcid":false,"given":"Ling","family":"Yu","sequence":"additional","affiliation":[{"name":"Functional Polymer Materials R&D and Engineering Application Technology Innovation Center of Hebei Province, Xingtai University, Xingtai 054001, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Sisi","family":"Wen","sequence":"additional","affiliation":[{"name":"Functional Polymer Materials R&D and Engineering Application Technology Innovation Center of Hebei Province, Xingtai University, Xingtai 054001, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Lisi","family":"Ba","sequence":"additional","affiliation":[{"name":"Functional Polymer Materials R&D and Engineering Application Technology Innovation Center of Hebei Province, Xingtai University, Xingtai 054001, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Long","family":"Ao","sequence":"additional","affiliation":[{"name":"Functional Polymer Materials R&D and Engineering Application Technology Innovation Center of Hebei Province, Xingtai University, Xingtai 054001, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Zhiju","family":"Zhao","sequence":"additional","affiliation":[{"name":"Functional Polymer Materials R&D and Engineering Application Technology Innovation Center of Hebei Province, Xingtai University, Xingtai 054001, China"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"1968","published-online":{"date-parts":[[2025,7,23]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"9237","DOI":"10.1021\/acs.chemrev.6b00153","article-title":"Functional short-bite ligands: Synthesis, coordination chemistry, and applications of N-functionalized bis(diaryl\/dialkylphosphino)amine-type ligands","volume":"116","author":"Fliedel","year":"2016","journal-title":"Chem. Rev."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"11857","DOI":"10.1021\/acs.chemrev.9b00383","article-title":"Reductive amination in the synthesis of pharmaceuticals","volume":"119","author":"Afanasyev","year":"2019","journal-title":"Chem. Rev."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"10954","DOI":"10.1039\/D4SC01813C","article-title":"Atomically dispersed cobalt catalysts for tandem synthesis of primary benzylamines from oxidized b-O-4 segments","volume":"15","author":"Luan","year":"2024","journal-title":"Chem. Sci."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"150","DOI":"10.1002\/anie.201106737","article-title":"Platinum-catalyzed direct amination of allylic alcohols with aqueous ammonia: Selective synthesis of primary allylamines","volume":"51","author":"Das","year":"2012","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"8661","DOI":"10.1002\/anie.200803229","article-title":"Selective synthesis of primary amines directly from alcohols and ammonia","volume":"47","author":"Gunanathan","year":"2008","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"7599","DOI":"10.1002\/anie.201103199","article-title":"Improved rutheniumcatalyzed amination of alcohols with ammonia: Synthesis of diamines and amino esters","volume":"50","author":"Imm","year":"2011","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"794","DOI":"10.2174\/1385272820666160525123907","article-title":"Recent advances in the reduction of nitro compounds by heterogenous catalysts","volume":"21","author":"Goksu","year":"2017","journal-title":"Curr. Org. Chem."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"842","DOI":"10.1002\/cssc.201601843","article-title":"Selective hydrogenation of nitriles to primary amines by using a cobalt phosphine catalyst","volume":"10","author":"Adam","year":"2017","journal-title":"ChemSusChem"},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"2149","DOI":"10.1007\/s10562-016-1822-6","article-title":"Efficient reduction of C-N multiple bonds catalyzed by magnetically retrievable magnetite nanoparticles with sodium borohydride","volume":"146","author":"Kumari","year":"2016","journal-title":"Catal. Lett."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"1662","DOI":"10.1002\/anie.201108155","article-title":"Two iron catalysts are better than one: A general and convenient reduction of aromatic and aliphatic primary amides","volume":"51","author":"Das","year":"2012","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"699","DOI":"10.1038\/s41467-019-08577-4","article-title":"N-formyl-stabilizing quasi-catalytic species afford rapid and selective solvent-free amination of biomass-derived feedstocks","volume":"10","author":"Li","year":"2019","journal-title":"Nat. Commun."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"9047","DOI":"10.1039\/D2SC01596J","article-title":"Nanoparticles and single atoms of cobalt synergistically enabled low-temperature reductive amination of carbonyl compounds","volume":"13","author":"Zheng","year":"2022","journal-title":"Chem. Sci."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"7763","DOI":"10.1021\/acscatal.0c01872","article-title":"Ambient-temperature synthesis of primary amines via reductive amination of carbonyl compounds","volume":"10","author":"Xie","year":"2020","journal-title":"ACS Catal."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"355","DOI":"10.1021\/jacs.7b10496","article-title":"Direct asymmetric ruthenium-catalyzed reductive amination of alkyl-aryl ketones with ammonia and hydrogen","volume":"140","author":"Hermsen","year":"2018","journal-title":"J. Am. Chem. Soc."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"311","DOI":"10.1021\/acscatal.9b03744","article-title":"Organonitrogen chemicals from oxygen-containing feedstock over heterogeneous catalysts","volume":"10","author":"Wang","year":"2019","journal-title":"ACS Catal."},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"13554","DOI":"10.1021\/jacs.7b07368","article-title":"Cobalt-catalyzed and lewis acid-assisted nitrile hydrogenation to primary amines: A combined effort","volume":"139","author":"Tokmic","year":"2017","journal-title":"J. Am. Chem. Soc."},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"921","DOI":"10.1002\/cctc.201402996","article-title":"Selective synthesis of primary amines by reductive amination of ketones with ammonia over supported Pt catalysts","volume":"7","author":"Nakamura","year":"2015","journal-title":"ChemCatChem"},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"3050","DOI":"10.1002\/anie.201610964","article-title":"Production of primary amines by reductive amination of biomass-derived aldehydes\/ketones","volume":"56","author":"Liang","year":"2017","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"11493","DOI":"10.1021\/jacs.7b04481","article-title":"Electronic effect of ruthenium nanoparticles on efficient reductive amination of carbonyl compounds","volume":"139","author":"Komanoya","year":"2017","journal-title":"J. Am. Chem. Soc."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"487","DOI":"10.1039\/C5GC01352F","article-title":"Reductive amination of furfural to furfurylamine using aqueous ammonia solution and molecular hydrogen: An environmentally friendly approach","volume":"18","author":"Chatterjee","year":"2016","journal-title":"Green Chem."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"2055","DOI":"10.1021\/ol0200605","article-title":"Synthesis of primary amines:\u2009 first homogeneously catalyzed reductive amination with ammonia","volume":"4","author":"Gross","year":"2002","journal-title":"Org. Lett."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"4123","DOI":"10.1038\/s41467-018-06416-6","article-title":"Simple ruthenium-catalyzed reductive amination enables the synthesis of a broad range of primary amines","volume":"9","author":"Senthamarai","year":"2018","journal-title":"Nat. Commun."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"2292","DOI":"10.1021\/jacs.7b12212","article-title":"Ni-catalyzed carbon\u2013carbon bond-forming reductive amination","volume":"140","author":"Heinz","year":"2018","journal-title":"J. Am. Chem. Soc."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"326","DOI":"10.1126\/science.aan6245","article-title":"MOF-derived cobalt nanoparticles catalyze a general synthesis of amines","volume":"358","author":"Jagadeesh","year":"2017","journal-title":"Science"},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"2360","DOI":"10.1002\/cssc.202100553","article-title":"Co-catalyzed synthesis of primary amines via reductive amination employing hydrogen under very mild conditions","volume":"14","author":"Elfinger","year":"2021","journal-title":"ChemSusChem"},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"5064","DOI":"10.1002\/anie.201812100","article-title":"Reusable nickel nanoparticles-catalyzed reductive amination for selective synthesis of primary amines","volume":"58","author":"Murugesan","year":"2019","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"71","DOI":"10.1038\/s41929-018-0202-6","article-title":"Generalsynthesis of primary amines via reductive amination employing a reusable nickel catalyst","volume":"2","author":"Hahn","year":"2019","journal-title":"Nat. Catal."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"3110","DOI":"10.1002\/cssc.202000856","article-title":"The synthesis of primary amines through reductive amination employing an iron catalyst","volume":"13","author":"Bauer","year":"2020","journal-title":"ChemSusChem"},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"75","DOI":"10.1016\/j.catcom.2007.05.016","article-title":"Characterization and reductive amination of cyclohexanol and cyclohexanone over Cu\/ZrO2 catalysts","volume":"9","author":"Chary","year":"2008","journal-title":"Catal. Commun."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"158280","DOI":"10.1016\/j.cej.2024.158280","article-title":"Enhanced efficiency and stability of Cs-modified Ni-based catalysts for selective synthesis of primary amines","volume":"503","author":"Zhang","year":"2025","journal-title":"Chem. Eng. J."},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"5430","DOI":"10.1039\/D4CY00536H","article-title":"Supported Fe catalysts prepared through layered double hydroxides for primary amine synthesis by reductive amination of carbonyl compounds","volume":"14","author":"Kita","year":"2024","journal-title":"Catal. Sci. Technol."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"14326","DOI":"10.1021\/jacs.4c18611","article-title":"Highly active and air-stable iron phosphide catalyst for reductive amination of carbonyl compounds enabled by metal-support synergy","volume":"147","author":"Tsuda","year":"2025","journal-title":"J. Am. Chem. Soc."},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"501","DOI":"10.1021\/jacsau.1c00125","article-title":"Single-crystal cobalt phosphide nanorods as a high-performance catalyst for reductive amination of carbonyl compounds","volume":"1","author":"Sheng","year":"2021","journal-title":"JACS Au"},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"2","DOI":"10.1002\/anie.202008261","article-title":"Cobalt Nanoparticles-catalyzed widely applicable successive C-C bond cleavage in alcohols to access esters","volume":"59","author":"Luo","year":"2020","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"6060","DOI":"10.1002\/anie.201200963","article-title":"Br\u00f8nsted acid activation strategy in transition-metal catalyzed asymmetric hydrogenation of N-unprotected imines, enamines, and N-heteroaromatic compounds","volume":"51","author":"Yu","year":"2012","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"6967","DOI":"10.1021\/ja9021683","article-title":"Metal-br\u00f8nsted acid cooperative catalysis for asymmetric reductive amination","volume":"131","author":"Li","year":"2009","journal-title":"J. Am. Chem. Soc."},{"key":"ref_37","first-page":"87","article-title":"A remarkable solvent effect on reductive amination of ketones","volume":"454","author":"Song","year":"2018","journal-title":"Mol. Catal."}],"container-title":["Molecules"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1420-3049\/30\/15\/3089\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,9]],"date-time":"2025-10-09T18:14:50Z","timestamp":1760033690000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1420-3049\/30\/15\/3089"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2025,7,23]]},"references-count":37,"journal-issue":{"issue":"15","published-online":{"date-parts":[[2025,8]]}},"alternative-id":["molecules30153089"],"URL":"https:\/\/doi.org\/10.3390\/molecules30153089","relation":{},"ISSN":["1420-3049"],"issn-type":[{"value":"1420-3049","type":"electronic"}],"subject":[],"published":{"date-parts":[[2025,7,23]]}}}