{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,2,20]],"date-time":"2026-02-20T16:51:32Z","timestamp":1771606292048,"version":"3.50.1"},"reference-count":35,"publisher":"Wiley","issue":"17","license":[{"start":{"date-parts":[[2023,12,6]],"date-time":"2023-12-06T00:00:00Z","timestamp":1701820800000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by-nc\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100002347","name":"Bundesministerium f\u00fcr Bildung und Forschung","doi-asserted-by":"publisher","award":["02WER1528 A\u2010E"],"award-info":[{"award-number":["02WER1528 A\u2010E"]}],"id":[{"id":"10.13039\/501100002347","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100002347","name":"Bundesministerium f\u00fcr Bildung und Forschung","doi-asserted-by":"publisher","award":["03SF0566B0"],"award-info":[{"award-number":["03SF0566B0"]}],"id":[{"id":"10.13039\/501100002347","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Small"],"published-print":{"date-parts":[[2024,4]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>A novel gaseous synthesis route to oxymethylene dimethyl ethers (OMEn, n = 3\u22125) starting from CO<jats:sub>2<\/jats:sub> and green H<jats:sub>2<\/jats:sub> by using molecular formaldehyde (FA) and dimethyl ether (DME) is presented. The anhydrous reaction runs in a pressure free, gaseous, and continuous reaction setup. Hetero\u2010geneous cata\u2010lysts including zeolites and ion exchange resins (IER) are investigated, if they catalyze this reaction. While IER is almost inactive, zeolites with a 3D pore structure and an acidity exceeding \u03c1<jats:sub>m,H+<\/jats:sub>(N<jats:sub>H3,ads<\/jats:sub>) = 250 \u00b5mol\u00b7gcat.<jats:sup>\u22121<\/jats:sup> proved to be catalytically active. DME conversions of up to 2.76 mol\u2010% are observed. The observed product gas stream compositions confirm thermo\u2010dynamic considerations with back reactions \/ OMEn decomposition occurring as part of the equilibria under the investigated reaction conditions (90\u2026180 \u00b0C). However, feed gas ratio variations (FA:DME = 1:2 to 1:9.5) highlighted the possibility to shift the product selectivity in favor of OMEn and suppress FA disproportionation to methyl formate. FA trimerization to trioxane is almost completely suppressed by running the reaction at 120 \u00b0C. The results presented here provide an important and unprecedented contribution to understand the complex reaction network in the OMEn synthesis reaction necessary to establish an energy efficient sustainable OMEn production process.<\/jats:p>","DOI":"10.1002\/smll.202306862","type":"journal-article","created":{"date-parts":[[2023,12,6]],"date-time":"2023-12-06T18:21:38Z","timestamp":1701886898000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":4,"title":["Continuous Anhydrous Synthesis of Oxymethylene Dimethyl Ethers by Reaction of Dimethyl Ether with Molecular Formaldehyde"],"prefix":"10.1002","volume":"20","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-8414-6282","authenticated-orcid":false,"given":"Andreas","family":"Billion","sequence":"first","affiliation":[{"name":"Institut f\u00fcr Anorganische und Analytische Chemie and Freiburger Materialforschungszentrum FMF Albert\u2010Ludwigs\u2010Universit\u00e4t Freiburg  Albertstr 21 79104 Freiburg Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Jonas","family":"Schulte","sequence":"additional","affiliation":[{"name":"Institut f\u00fcr Anorganische und Analytische Chemie and Freiburger Materialforschungszentrum FMF Albert\u2010Ludwigs\u2010Universit\u00e4t Freiburg  Albertstr 21 79104 Freiburg Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Andreas","family":"Vogel","sequence":"additional","affiliation":[{"name":"Institut f\u00fcr Anorganische und Analytische Chemie and Freiburger Materialforschungszentrum FMF Albert\u2010Ludwigs\u2010Universit\u00e4t Freiburg  Albertstr 21 79104 Freiburg Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Felix","family":"Hilfinger","sequence":"additional","affiliation":[{"name":"Institut f\u00fcr Anorganische und Analytische Chemie and Freiburger Materialforschungszentrum FMF Albert\u2010Ludwigs\u2010Universit\u00e4t Freiburg  Albertstr 21 79104 Freiburg Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7182-4387","authenticated-orcid":false,"given":"Ingo","family":"Krossing","sequence":"additional","affiliation":[{"name":"Institut f\u00fcr Anorganische und Analytische Chemie and Freiburger Materialforschungszentrum FMF Albert\u2010Ludwigs\u2010Universit\u00e4t Freiburg  Albertstr 21 79104 Freiburg Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2023,12,6]]},"reference":[{"key":"e_1_2_8_1_1","doi-asserted-by":"publisher","DOI":"10.1021\/acssuschemeng.9b02895"},{"key":"e_1_2_8_2_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jced.7b00718"},{"key":"e_1_2_8_3_1","doi-asserted-by":"publisher","DOI":"10.1007\/s38313-016-0163-6"},{"key":"e_1_2_8_3_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.apenergy.2019.02.035"},{"key":"e_1_2_8_4_1","doi-asserted-by":"publisher","DOI":"10.1021\/ie060131u"},{"key":"e_1_2_8_4_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.cherd.2011.09.014"},{"key":"e_1_2_8_4_3","doi-asserted-by":"publisher","DOI":"10.1021\/acs.iecr.5b04046"},{"key":"e_1_2_8_4_4","doi-asserted-by":"publisher","DOI":"10.1021\/acs.iecr.8b06044"},{"key":"e_1_2_8_5_1","doi-asserted-by":"publisher","DOI":"10.1039\/D1SE01270C"},{"key":"e_1_2_8_6_1","doi-asserted-by":"publisher","DOI":"10.1021\/acssuschemeng.2c00004"},{"key":"e_1_2_8_6_2","doi-asserted-by":"publisher","DOI":"10.1039\/D2RE00508E"},{"key":"e_1_2_8_6_3","doi-asserted-by":"publisher","DOI":"10.1002\/cctc.201900502"},{"key":"e_1_2_8_6_4","doi-asserted-by":"publisher","DOI":"10.1002\/chem.202203776"},{"key":"e_1_2_8_6_5","doi-asserted-by":"publisher","DOI":"10.1016\/j.seppur.2021.119538"},{"key":"e_1_2_8_7_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.iecr.2c00790"},{"key":"e_1_2_8_8_1","doi-asserted-by":"publisher","DOI":"10.1002\/cite.202100173"},{"key":"e_1_2_8_9_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.cattod.2022.07.015"},{"key":"e_1_2_8_10_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.catcom.2018.02.013"},{"key":"e_1_2_8_11_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.7b00701"},{"key":"e_1_2_8_11_2","doi-asserted-by":"publisher","DOI":"10.1002\/cctc.201900115"},{"key":"e_1_2_8_12_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.iecr.8b05577"},{"key":"e_1_2_8_12_2","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3773(20000616)39:12<2102::AID-ANIE2102>3.0.CO;2-E"},{"key":"e_1_2_8_13_1","doi-asserted-by":"publisher","DOI":"10.1007\/s10562-022-04265-z"},{"key":"e_1_2_8_14_1","doi-asserted-by":"publisher","DOI":"10.1002\/cctc.202200258"},{"key":"e_1_2_8_15_1","doi-asserted-by":"publisher","DOI":"10.1039\/C6RE00145A"},{"key":"e_1_2_8_16_1","doi-asserted-by":"publisher","DOI":"10.1039\/C7SE00053G"},{"key":"e_1_2_8_17_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.fuel.2019.115925"},{"key":"e_1_2_8_18_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.apcatb.2017.06.007"},{"key":"e_1_2_8_19_1","doi-asserted-by":"publisher","DOI":"10.1021\/ie301490q"},{"key":"e_1_2_8_20_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.iecr.0c05780"},{"key":"e_1_2_8_21_1","volume-title":"Formaldehyde","author":"Walker J. F.","year":"1964"},{"key":"e_1_2_8_21_2","doi-asserted-by":"publisher","DOI":"10.1007\/s10934-022-01340-z"},{"key":"e_1_2_8_22_1","doi-asserted-by":"publisher","DOI":"10.1002\/cctc.202300844"},{"key":"e_1_2_8_23_1","volume-title":"Atlas of Zeolite Framework Types","author":"McCusker L.","year":"2007"},{"key":"e_1_2_8_24_1","unstructured":"Effect of the Catalyst Adjustment Time: Interestingly catalytic measurements performed without a previous catalyst adjustment time at higher feed gas flows but directly at these reaction conditions (FA:DME = 1.0:2.0 reaction temperature: 90\u00a0\u00b0C flow rate of reactants(DME FA) = 1.0 g\u2219h\u22121) exhibited a significantly reduced catalytic activity (Figures 23 and 24 Supporting Information). Here the highest conversions amounted to XDME 300\u00a0mg = 1.41% (WHSV 5.2 h\u22121) and XDME 500\u00a0mg = 1.22% (WHSV 3.1 h\u22121). We note that the catalytic performance did not approach the previously observed conversion of XDME = 2.56% even after 19\u00a0h. Thus the pretreatment respectively with the feed gas flow has a significant influence on the catalytic activity. However IR spectroscopic investigations of the zeolites after catalysis and comparison with a blank sample of H\u2010BEA\u2010360 prior to catalysis did not yield any insights that could potentially explain the observed variations in catalytic activity (Figure S6 Supporting Information). Instead the catalytic results of H\u2010BEA\u2010360 (500\u00a0mg WHSV 3.1 h\u22121) sssindicate an initial phase of equilibrium adjustment (Figure S24 Supporting Information). After ten catalyst measurements a bypass measurement was performed to verify the feed gas flow and composition. Meanwhile the reactor was flushed with nitrogen for 20\u00a0min. The consecutive measurement also exhibits an increased conversion XDME 500\u00a0mg run11 = 1.21% compared to XDME 500\u00a0mg run10 = 1.02%. The same trend was observed after another ten measurements (XDME 500\u00a0mg run20 = 1.06% vs XDME 500\u00a0mg run21 = 1.24%)."}],"container-title":["Small"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/smll.202306862","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2024,4,26]],"date-time":"2024-04-26T02:16:16Z","timestamp":1714097776000},"score":1,"resource":{"primary":{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/10.1002\/smll.202306862"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2023,12,6]]},"references-count":35,"journal-issue":{"issue":"17","published-print":{"date-parts":[[2024,4]]}},"alternative-id":["10.1002\/smll.202306862"],"URL":"https:\/\/doi.org\/10.1002\/smll.202306862","archive":["Portico"],"relation":{},"ISSN":["1613-6810","1613-6829"],"issn-type":[{"value":"1613-6810","type":"print"},{"value":"1613-6829","type":"electronic"}],"subject":[],"published":{"date-parts":[[2023,12,6]]},"assertion":[{"value":"2023-08-10","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2023-12-06","order":2,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}],"article-number":"2306862"}}