{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,28]],"date-time":"2026-09-28T14:02:00Z","timestamp":1790604120667,"version":"4.1.0"},"reference-count":49,"publisher":"Wiley","issue":"40","license":[{"start":{"date-parts":[[2026,8,5]],"date-time":"2026-08-05T00:00:00Z","timestamp":1785888000000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by\/4.0\/"},{"start":{"date-parts":[[2026,8,5]],"date-time":"2026-08-05T00:00:00Z","timestamp":1785888000000},"content-version":"tdm","delay-in-days":0,"URL":"http:\/\/doi.wiley.com\/10.1002\/tdm_license_1.1"}],"funder":[{"DOI":"10.13039\/501100001711","name":"Schweizerischer Nationalfonds zur F\u00f6rderung der Wissenschaftlichen Forschung","doi-asserted-by":"publisher","award":["CRSII5\u2010183495"],"award-info":[{"award-number":["CRSII5\u2010183495"]}],"id":[{"id":"10.13039\/501100001711","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Angew Chem Int Ed"],"published-print":{"date-parts":[[2026,9,28]]},"abstract":"<jats:title>ABSTRACT<\/jats:title>\n                  <jats:p>\n                    The synergistic Cu\u2013metal oxide (Cu\u2013MO\n                    <jats:sub>x<\/jats:sub>\n                    ) interface is critical for selective CO\n                    <jats:sub>2<\/jats:sub>\n                    hydrogenation to methanol, yet its mechanistic function, the central, long\u2010debated feature of industrial Cu\/ZnO\/Al\n                    <jats:sub>2<\/jats:sub>\n                    O\n                    <jats:sub>3<\/jats:sub>\n                    , remains ambiguous. Using\n                    <jats:italic>operando<\/jats:italic>\n                    transient DRIFTS\u2010SSITKA, we elucidate the roles of M\n                    <jats:sup>+<\/jats:sup>\n                    sites (Zn\n                    <jats:sup>2+<\/jats:sup>\n                    , Ga\n                    <jats:sup>3+<\/jats:sup>\n                    , and In\n                    <jats:sup>3+<\/jats:sup>\n                    ) on model Cu\u2500M\/SiO\n                    <jats:sub>2<\/jats:sub>\n                    catalysts prepared by surface organometallic chemistry (SOMC). X\u2010ray absorption spectroscopy reveals that these promoters restructure from alloys after reduction to cationic species at the interface under reaction conditions. We find the promoter's electronic effect on formate bond strengths provides quantitative descriptors for both activity and selectivity. All catalysts follow a common formate spillover mechanism, with methoxy hydrogenation\/desorption as the rate\u2010limiting step. The intrinsic CH\n                    <jats:sub>3<\/jats:sub>\n                    OH formation rate follows a Sabatier\u2010type volcano with C\u2500O bond strength, while selectivity correlates linearly with C\u2500H bond strength (a proxy for the formate decomposition barrier). Cu\u2500Ga\/SiO\n                    <jats:sub>2<\/jats:sub>\n                    shows the fastest spillover, suppressing CO formation and yielding the highest selectivity; Cu\u2500Zn\/SiO\n                    <jats:sub>2<\/jats:sub>\n                    has optimal binding for the highest activity; In\n                    <jats:sup>3+<\/jats:sup>\n                    binds formate too strongly, creating a kinetic trap on the strong\u2010binding side of the volcano. These findings bring mechanistic clarity to the debated Cu\u2500Zn(O) synergy, showing selectivity is governed by a balance of electronic stabilization and spillover dynamics.\n                  <\/jats:p>","DOI":"10.1002\/anie.2693293","type":"journal-article","created":{"date-parts":[[2026,8,5]],"date-time":"2026-08-05T14:04:13Z","timestamp":1785938653000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Key Drivers of Activity and Selectivity in Cu\u2010Based Catalysts for Methanol Synthesis From CO\n                    <sub>2<\/sub>\n                    : Insights From Atomically Dispersed Promoters"],"prefix":"10.1002","volume":"65","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-4225-8205","authenticated-orcid":false,"given":"Nat","family":"Phongprueksathat","sequence":"first","affiliation":[{"name":"Catalysis Engineering Department of Chemical Engineering Delft University of Technology  Delft The Netherlands"},{"name":"Catalysis Engineering Van \u2019t Hoff Institute for Molecular Sciences University of Amsterdam  Amsterdam The Netherlands"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4717-5767","authenticated-orcid":false,"given":"Gina","family":"Noh","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Applied Biosciences ETH Z\u00fcrich  Zurich Switzerland"},{"name":"Department of Chemical Engineering The Pennsylvania State University  Pennsylvania Pennsylvania USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8605-3669","authenticated-orcid":false,"given":"Scott R.","family":"Docherty","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Applied Biosciences ETH Z\u00fcrich  Zurich Switzerland"},{"name":"Material Science Department of Chemistry Columbia University  New York New York USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Damian Vico","family":"van Berkel","sequence":"additional","affiliation":[{"name":"Catalysis Engineering Department of Chemical Engineering Delft University of Technology  Delft The Netherlands"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0007-4880-0348","authenticated-orcid":false,"given":"Yannik","family":"Stiefel","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Applied Biosciences ETH Z\u00fcrich  Zurich Switzerland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9660-3890","authenticated-orcid":false,"given":"Christophe","family":"Cop\u00e9ret","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Applied Biosciences ETH Z\u00fcrich  Zurich Switzerland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7778-4008","authenticated-orcid":false,"given":"Atsushi","family":"Urakawa","sequence":"additional","affiliation":[{"name":"Catalysis Engineering Department of Chemical Engineering Delft University of Technology  Delft The Netherlands"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2026,8,5]]},"reference":[{"key":"e_1_2_8_2_1","doi-asserted-by":"publisher","DOI":"10.1002\/9783527805662"},{"key":"e_1_2_8_3_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201204995"},{"key":"e_1_2_8_4_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.3c00148"},{"key":"e_1_2_8_5_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41467\u2010020\u201017631\u20105"},{"key":"e_1_2_8_6_1","doi-asserted-by":"publisher","DOI":"10.1023\/A:1023588322846"},{"key":"e_1_2_8_7_1","doi-asserted-by":"publisher","DOI":"10.1126\/science.1219831"},{"key":"e_1_2_8_8_1","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201411581"},{"key":"e_1_2_8_9_1","doi-asserted-by":"publisher","DOI":"10.1126\/science.aal3573"},{"key":"e_1_2_8_10_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202200301"},{"key":"e_1_2_8_11_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.coche.2016.02.002"},{"key":"e_1_2_8_12_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41929\u2010021\u201000625\u2010x"},{"key":"e_1_2_8_13_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41929\u2010021\u201000638\u20106"},{"key":"e_1_2_8_14_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.1c02555"},{"key":"e_1_2_8_15_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.jcat.2020.04.028"},{"key":"e_1_2_8_16_1","doi-asserted-by":"publisher","DOI":"10.1039\/D0SC00465K"},{"key":"e_1_2_8_17_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacsau.1c00021"},{"key":"e_1_2_8_18_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacsau.3c00319"},{"key":"e_1_2_8_19_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jpcc.9b09631"},{"key":"e_1_2_8_20_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.8b05595"},{"key":"e_1_2_8_21_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202100672"},{"key":"e_1_2_8_22_1","doi-asserted-by":"publisher","DOI":"10.1039\/d2sc03107h"},{"key":"e_1_2_8_23_1","doi-asserted-by":"publisher","DOI":"10.1021\/cs501264f"},{"key":"e_1_2_8_24_1","doi-asserted-by":"publisher","DOI":"10.1039\/C4AY00571F"},{"key":"e_1_2_8_25_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.chemolab.2014.10.003"},{"key":"e_1_2_8_26_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201610166"},{"key":"e_1_2_8_27_1","doi-asserted-by":"publisher","DOI":"10.1002\/cssc.201900134"},{"key":"e_1_2_8_28_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.9b02412"},{"key":"e_1_2_8_29_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201908060"},{"key":"e_1_2_8_30_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202006921"},{"key":"e_1_2_8_31_1","doi-asserted-by":"publisher","DOI":"10.1038\/srep41207"},{"key":"e_1_2_8_32_1","doi-asserted-by":"publisher","DOI":"10.1002\/cctc.202501115"},{"key":"e_1_2_8_33_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jpcc.2c02995"},{"key":"e_1_2_8_34_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41467\u2010020\u201016342\u20101"},{"key":"e_1_2_8_35_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.8b08505"},{"key":"e_1_2_8_36_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202423281"},{"key":"e_1_2_8_37_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202303939"},{"key":"e_1_2_8_38_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.jcat.2019.10.013"},{"key":"e_1_2_8_39_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202420126"},{"key":"e_1_2_8_40_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.5c04835"},{"key":"e_1_2_8_41_1","doi-asserted-by":"publisher","DOI":"10.1039\/b800519b"},{"key":"e_1_2_8_42_1","doi-asserted-by":"publisher","DOI":"10.1366\/0003702944029893"},{"key":"e_1_2_8_43_1","doi-asserted-by":"publisher","DOI":"10.1039\/ft9918702795"},{"key":"e_1_2_8_44_1","doi-asserted-by":"publisher","DOI":"10.1039\/ft9918702785"},{"key":"e_1_2_8_45_1","doi-asserted-by":"publisher","DOI":"10.1039\/FT9928802257"},{"key":"e_1_2_8_46_1","doi-asserted-by":"publisher","DOI":"10.1006\/jcat.1995.1187"},{"key":"e_1_2_8_47_1","doi-asserted-by":"publisher","DOI":"10.1016\/0926\u2010860X(92)80041\u2010A"},{"key":"e_1_2_8_48_1","doi-asserted-by":"publisher","DOI":"10.1002\/cplu.201200086"},{"key":"e_1_2_8_49_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.ces.2007.06.009"},{"key":"e_1_2_8_50_1","doi-asserted-by":"publisher","DOI":"10.1039\/D3CC05973A"}],"container-title":["Angewandte Chemie International Edition"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.2693293","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/full-xml\/10.1002\/anie.2693293","content-type":"application\/xml","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.2693293","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,9,28]],"date-time":"2026-09-28T13:21:02Z","timestamp":1790601662000},"score":1,"resource":{"primary":{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/10.1002\/anie.2693293"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,8,5]]},"references-count":49,"journal-issue":{"issue":"40","published-print":{"date-parts":[[2026,9,28]]}},"alternative-id":["10.1002\/anie.2693293"],"URL":"https:\/\/doi.org\/10.1002\/anie.2693293","archive":["Portico"],"relation":{},"ISSN":["1433-7851","1521-3773"],"issn-type":[{"value":"1433-7851","type":"print"},{"value":"1521-3773","type":"electronic"}],"subject":[],"published":{"date-parts":[[2026,8,5]]},"assertion":[{"value":"2026-01-25","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2026-06-30","order":2,"name":"accepted","label":"Accepted","group":{"name":"publication_history","label":"Publication History"}},{"value":"2026-08-05","order":3,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}],"article-number":"e2693293"}}