{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,8,15]],"date-time":"2026-08-15T04:28:25Z","timestamp":1786768105044,"version":"build-2736575974"},"reference-count":78,"publisher":"Wiley","issue":"15","license":[{"start":{"date-parts":[[2026,7,31]],"date-time":"2026-07-31T00:00:00Z","timestamp":1785456000000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"},{"start":{"date-parts":[[2026,7,31]],"date-time":"2026-07-31T00:00:00Z","timestamp":1785456000000},"content-version":"tdm","delay-in-days":0,"URL":"http:\/\/doi.wiley.com\/10.1002\/tdm_license_1.1"}],"content-domain":{"domain":["chemistry-europe.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["ChemPhysChem"],"published-print":{"date-parts":[[2026,8,14]]},"abstract":"<jats:p>\n                    In this work, we investigated silicon disubstituted cyclo[18]carbon as a metal\u2010free catalyst for nitrogen activation and ammonia synthesis using density functional theory at the \u03c9B97XD\/def2\u2010TZVPP level. A systematic comparison of the structural features of pristine C\n                    <jats:sub>18<\/jats:sub>\n                    , monosubstituted C\n                    <jats:sub>17<\/jats:sub>\n                    Si, and nine C\n                    <jats:sub>16<\/jats:sub>\n                    Si\n                    <jats:sub>2<\/jats:sub>\n                    isomers (C\n                    <jats:sub>16<\/jats:sub>\n                    Si\n                    <jats:sub>2<\/jats:sub>\n                    (0)\u2013C\n                    <jats:sub>16<\/jats:sub>\n                    Si\n                    <jats:sub>2<\/jats:sub>\n                    (8)) identifies C\n                    <jats:sub>16<\/jats:sub>\n                    Si\n                    <jats:sub>2<\/jats:sub>\n                    (8) as the most stable configuration, attributed to the maximum Si\u2013Si separation and minimal distortion of the conjugated carbon framework. Electronic structure analysis indicates that dual Si substitution creates active sites that are highly electron\u2010deficient and a more symmetrically distributed reactive environment, thereby promoting strong N\n                    <jats:sub>2<\/jats:sub>\n                    adsorption and effective activation via Si \u2192 N\n                    <jats:sub>2<\/jats:sub>\n                    back\u2010donation. The activated C\n                    <jats:sub>16<\/jats:sub>\n                    Si\n                    <jats:sub>2<\/jats:sub>\n                    \u2013N\n                    <jats:sub>2<\/jats:sub>\n                    complex undergoes stepwise hydrogenation via C\n                    <jats:sub>16<\/jats:sub>\n                    Si\n                    <jats:sub>2<\/jats:sub>\n                    \u2013NH\n                    <jats:sub>2<\/jats:sub>\n                    and C\n                    <jats:sub>16<\/jats:sub>\n                    Si\n                    <jats:sub>2<\/jats:sub>\n                    \u2013(NH\n                    <jats:sub>2<\/jats:sub>\n                    )\n                    <jats:sub>2<\/jats:sub>\n                    intermediates, ultimately yielding two NH\n                    <jats:sub>3<\/jats:sub>\n                    molecules through an overall energetically favorable pathway. Importantly, the resulting C\n                    <jats:sub>16<\/jats:sub>\n                    Si\n                    <jats:sub>2<\/jats:sub>\n                    \u2013H\n                    <jats:sub>2<\/jats:sub>\n                    adduct re\u2010enters the catalytic cycle by reacting with the remaining C\n                    <jats:sub>16<\/jats:sub>\n                    Si\n                    <jats:sub>2<\/jats:sub>\n                    \u2013N\n                    <jats:sub>2<\/jats:sub>\n                    , producing C\n                    <jats:sub>16<\/jats:sub>\n                    Si\n                    <jats:sub>2<\/jats:sub>\n                    \u2013(NH)\n                    <jats:sub>2<\/jats:sub>\n                    and restoring the catalytic pathway, thereby establishing a self\u2010sustaining mechanism. Overall, our findings show that multisite silicon engineering of cyclo[18]carbon frameworks is an effective strategy for developing efficient, metal\u2010free catalysts for ammonia synthesis under mild conditions.\n                  <\/jats:p>","DOI":"10.1002\/cphc.70529","type":"journal-article","created":{"date-parts":[[2026,7,31]],"date-time":"2026-07-31T10:19:17Z","timestamp":1785493157000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Catalytic Ammonia Synthesis Over Metal\u2010Free Silicon Disubstituted Cyclo[18]carbon: A Density Functional Theory Study"],"prefix":"10.1002","volume":"27","author":[{"given":"Anu","family":"Arora","sequence":"first","affiliation":[{"name":"Department of Chemistry Ashoka University  Sonipat Haryana India"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Sobitri","family":"Sen","sequence":"additional","affiliation":[{"name":"Department of Chemistry Ashoka University  Sonipat Haryana India"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7366-8982","authenticated-orcid":false,"given":"Sourav","family":"Pal","sequence":"additional","affiliation":[{"name":"Department of Chemistry Ashoka University  Sonipat Haryana India"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2026,7,31]]},"reference":[{"key":"e_1_2_8_2_1","doi-asserted-by":"publisher","DOI":"10.1038\/ngeo325"},{"key":"e_1_2_8_3_1","doi-asserted-by":"publisher","DOI":"10.3390\/fuels3030026"},{"key":"e_1_2_8_4_1","doi-asserted-by":"publisher","DOI":"10.1039\/D0EE03808C"},{"key":"e_1_2_8_5_1","doi-asserted-by":"publisher","DOI":"10.1016\/S1872-2067(14)60118-2"},{"key":"e_1_2_8_6_1","doi-asserted-by":"publisher","DOI":"10.1007\/s00267-017-0831-6"},{"key":"e_1_2_8_7_1","doi-asserted-by":"publisher","DOI":"10.1002\/ep.11817"},{"key":"e_1_2_8_8_1","first-page":"333","article-title":"The Greenhouse Effect and Its Impacts on Environment","volume":"1","author":"Latake P. 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