{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,21]],"date-time":"2026-10-21T11:46:54Z","timestamp":1792583214032,"version":"4.5.0"},"reference-count":43,"publisher":"Wiley","license":[{"start":{"date-parts":[[2026,10,21]],"date-time":"2026-10-21T00:00:00Z","timestamp":1792540800000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"},{"start":{"date-parts":[[2026,10,21]],"date-time":"2026-10-21T00:00:00Z","timestamp":1792540800000},"content-version":"tdm","delay-in-days":0,"URL":"http:\/\/doi.wiley.com\/10.1002\/tdm_license_1.1"}],"funder":[{"DOI":"10.13039\/100000015","name":"U.S. Department of Energy","doi-asserted-by":"publisher","id":[{"id":"10.13039\/100000015","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/100006132","name":"Office of Science","doi-asserted-by":"publisher","id":[{"id":"10.13039\/100006132","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/100006151","name":"Basic Energy Sciences","doi-asserted-by":"publisher","id":[{"id":"10.13039\/100006151","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/100000161","name":"National Institute of Standards and Technology","doi-asserted-by":"publisher","id":[{"id":"10.13039\/100000161","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/100000190","name":"U.S. Department of Commerce","doi-asserted-by":"publisher","id":[{"id":"10.13039\/100000190","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Small"],"abstract":"ABSTRACT<\/jats:title>\n \n Methanol production by carbon dioxide hydrogenation is a promising route for supplying industrial fuel demands, but achieving high methanol selectivity remains challenging due to competing favorable reactions. Here, we investigate model Au\/In\n 2<\/jats:sub>\n O\n 3\u2010x<\/jats:sub>\n \/TiO\n 2<\/jats:sub>\n (110) catalysts to elucidate the roles of metal\u2010oxide and oxide\u2010oxide interactions in CO\n 2<\/jats:sub>\n conversion. Using a combination of ambient\u2010pressure X\u2010ray photoelectron spectroscopy (AP\u2010XPS), temperature\u2010programmed desorption (TPD), and catalytic measurements, we show that small coverages of Au (<0.15 monolayer) dispersed on In\n 2<\/jats:sub>\n O\n 3\u2010x<\/jats:sub>\n \/TiO\n 2<\/jats:sub>\n (110) significantly enhance both CO\n 2<\/jats:sub>\n and H\n 2<\/jats:sub>\n activation at low temperatures (300\u2013400 K). The Au\/In\n 2<\/jats:sub>\n O\n 3\u2010x<\/jats:sub>\n \/TiO\n 2<\/jats:sub>\n (110) systems exhibit superior catalytic performance, with the highest methanol selectivity (\u223c80\u201385%) and increased conversion rates compared to In\n 2<\/jats:sub>\n O\n 3\u2010x<\/jats:sub>\n \/TiO\n 2<\/jats:sub>\n (110) and Au\/TiO\n 2<\/jats:sub>\n (110). Spectroscopic results showed that Au nanoparticles promote the formation of oxygen vacancies and enhance CO\n 2<\/jats:sub>\n activation, without inducing the dissociation of methoxy and methanol. Reaction studies support a formate\u2010mediated reaction pathway, distinct from the CO\u2010mediated route observed on Au\/TiO\n 2<\/jats:sub>\n catalysts that leads to very low methanol selectivity. Oxide\u2010oxide interactions stabilized the partially reduced In\n 2<\/jats:sub>\n O\n 3\u2010x<\/jats:sub>\n , and prevented Au\u2010In alloy formation under CO\n 2<\/jats:sub>\n +H\n 2<\/jats:sub>\n conditions, preserving methanol selectivity. These findings highlight the importance of synergistic metal\u2194oxide\u2010oxide interactions when designing efficient catalysts for selective hydrogenation of CO\n 2<\/jats:sub>\n to methanol while minimizing the content of Au and In\n 2<\/jats:sub>\n O\n 3\u2010x<\/jats:sub>\n .\n <\/jats:p>","DOI":"10.1002\/smll.76353","type":"journal-article","created":{"date-parts":[[2026,10,21]],"date-time":"2026-10-21T11:31:32Z","timestamp":1792582292000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Au on in\n 2<\/sub>\n O\n 3\u2010x<\/sub>\n \/TiO\n 2<\/sub>\n (110): A Highly Active and Selective Catalyst for the Conversion of CO\n 2<\/sub>\n to Methanol"],"prefix":"10.1002","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-1616-5374","authenticated-orcid":false,"given":"Kasala Prabhakar","family":"Reddy","sequence":"first","affiliation":[{"name":"Chemistry Division Brookhaven National Laboratory Upton New York USA"},{"name":"Theiss Research La Jolla California USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0006-4311-5280","authenticated-orcid":false,"given":"Anas","family":"Mahmud","sequence":"additional","affiliation":[{"name":"Department of Chemistry SUNY Stony Brook Stony Brook New York USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-6236-5545","authenticated-orcid":false,"given":"Pedro J.","family":"Ram\u00edrez","sequence":"additional","affiliation":[{"name":"Facultad De Ciencias Universidad Central de Venezuela Caracas Venezuela"},{"name":"R&D Laboratories Zoneca\u2010CENEX Monterrey M\u00e9xico"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8528-859X","authenticated-orcid":false,"given":"Arephin","family":"Islam","sequence":"additional","affiliation":[{"name":"Chemistry Division Brookhaven National Laboratory Upton New York USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7793-685X","authenticated-orcid":false,"given":"Irene","family":"Barba\u2010Nieto","sequence":"additional","affiliation":[{"name":"Chemistry Division Brookhaven National Laboratory Upton New York USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0005-9229-2307","authenticated-orcid":false,"given":"Zahir","family":"Faruqi","sequence":"additional","affiliation":[{"name":"Department of Chemistry SUNY Stony Brook Stony Brook New York USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5283-9647","authenticated-orcid":false,"given":"Adrian","family":"Hunt","sequence":"additional","affiliation":[{"name":"National Synchrotron Light Source II Brookhaven National Laboratory Upton New York USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-4046-9722","authenticated-orcid":false,"given":"Iradwikanari","family":"Waluyo","sequence":"additional","affiliation":[{"name":"National Synchrotron Light Source II Brookhaven National Laboratory Upton New York USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5680-4214","authenticated-orcid":false,"given":"Jos\u00e9 A.","family":"Rodriguez","sequence":"additional","affiliation":[{"name":"Chemistry Division Brookhaven National Laboratory Upton New York USA"},{"name":"Department of Chemistry SUNY Stony Brook Stony Brook New York USA"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2026,10,21]]},"reference":[{"key":"e_1_2_8_2_1","doi-asserted-by":"publisher","DOI":"10.1007\/s11356\u2010024\u201034139\u20103"},{"key":"e_1_2_8_3_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.est.0c08674"},{"key":"e_1_2_8_4_1","doi-asserted-by":"publisher","DOI":"10.1002\/cctc.201500123"},{"key":"e_1_2_8_5_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41929\u2010017\u20100016\u2010y"},{"key":"e_1_2_8_6_1","doi-asserted-by":"publisher","DOI":"10.1039\/C5EE02657A"},{"key":"e_1_2_8_7_1","doi-asserted-by":"publisher","DOI":"10.1126\/science.adn9388"},{"key":"e_1_2_8_8_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201600943"},{"key":"e_1_2_8_9_1","doi-asserted-by":"crossref","DOI":"10.1126\/sciadv.aaz2060","article-title":"Rationally Designed Indium Oxide Catalysts for CO2 Hydrogenation to Methanol With Activity and Selectivity","volume":"6","author":"Shanahan D.","year":"2020","journal-title":"Science Advances"},{"key":"e_1_2_8_10_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.0c03665"},{"key":"e_1_2_8_11_1","doi-asserted-by":"publisher","DOI":"10.1021\/acsami.3c07166"},{"key":"e_1_2_8_12_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.4c01929"},{"key":"e_1_2_8_13_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.8b04848"},{"key":"e_1_2_8_14_1","doi-asserted-by":"publisher","DOI":"10.1039\/D0GC01597K"},{"key":"e_1_2_8_15_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.apcatb.2017.07.069"},{"key":"e_1_2_8_16_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41467\u2010019\u201011349\u20109"},{"key":"e_1_2_8_17_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.0c02120"},{"key":"e_1_2_8_18_1","doi-asserted-by":"publisher","DOI":"10.1021\/ar400182c"},{"key":"e_1_2_8_19_1","doi-asserted-by":"publisher","DOI":"10.1002\/cssc.201402645"},{"key":"e_1_2_8_20_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.9b00551"},{"key":"e_1_2_8_21_1","doi-asserted-by":"crossref","first-page":"14","DOI":"10.1016\/S1748-0132(07)70113-5","article-title":"Catalytic Activity of Au Nanoparticles","volume":"2","author":"Hvolb\u00e6k B.","year":"2007","journal-title":"Nanotoday"},{"key":"e_1_2_8_22_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.5b06150"},{"key":"e_1_2_8_23_1","doi-asserted-by":"publisher","DOI":"10.1002\/cssc.201402645"},{"key":"e_1_2_8_24_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.4c05837"},{"key":"e_1_2_8_25_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202306563"},{"key":"e_1_2_8_26_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.2c00207"},{"key":"e_1_2_8_27_1","doi-asserted-by":"publisher","DOI":"10.1021\/acsami.5c20054"},{"key":"e_1_2_8_28_1","doi-asserted-by":"crossref","first-page":"254","DOI":"10.1021\/jp807865w","article-title":"Sintering of Au Particles Supported on TiO2(110) During CO Oxidation","volume":"113","author":"Yang F.","year":"2009","journal-title":"Journal of Physical Chemistry C"},{"key":"e_1_2_8_29_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0039\u20106028(02)01873\u20103"},{"key":"e_1_2_8_30_1","doi-asserted-by":"publisher","DOI":"10.1126\/science.1135752"},{"key":"e_1_2_8_31_1","doi-asserted-by":"publisher","DOI":"10.1073\/pnas.0812604106"},{"key":"e_1_2_8_32_1","doi-asserted-by":"publisher","DOI":"10.1016\/0920\u20105861(95)00305\u20103"},{"key":"e_1_2_8_33_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jpcc.2c05715"},{"key":"e_1_2_8_34_1","doi-asserted-by":"publisher","DOI":"10.1021\/acsnano.2c09115"},{"key":"e_1_2_8_35_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.surfrep.2014.12.001"},{"key":"e_1_2_8_36_1","doi-asserted-by":"publisher","DOI":"10.1021\/jp501201b"},{"key":"e_1_2_8_37_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.susc.2006.02.011"},{"key":"e_1_2_8_38_1","doi-asserted-by":"crossref","first-page":"420","DOI":"10.1007\/s11244-016-0713-9","article-title":"The Role of Surface Defects in the Adsorption of Methanol on Fe3O4(001)","volume":"60","author":"Gamba O.","year":"2017","journal-title":"Topics in Catalysis"},{"key":"e_1_2_8_39_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jpcc.5c04763"},{"key":"e_1_2_8_40_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jpclett.4c01134"},{"key":"e_1_2_8_41_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.5c07042"},{"key":"e_1_2_8_42_1","doi-asserted-by":"publisher","DOI":"10.1021\/jp3089325"},{"key":"e_1_2_8_43_1","doi-asserted-by":"crossref","DOI":"10.1088\/1361-648X\/ae0bdb","article-title":"Novel Inverse Oxide\/Metal Catalysts for Methanol Synthesis: Impact of Oxide\u2013Metal Interactions and Reversible Morphological Changes","volume":"37","author":"Rodriguez J. A.","year":"2025","journal-title":"Journal of Physics\u2010Condensed Matter"},{"key":"e_1_2_8_44_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.energyfuels.2c02131"}],"container-title":["Small"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/smll.76353","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/full-xml\/10.1002\/smll.76353","content-type":"application\/xml","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/smll.76353","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,10,21]],"date-time":"2026-10-21T11:31:34Z","timestamp":1792582294000},"score":1,"resource":{"primary":{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/10.1002\/smll.76353"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,10,21]]},"references-count":43,"alternative-id":["10.1002\/smll.76353"],"URL":"https:\/\/doi.org\/10.1002\/smll.76353","archive":["Portico"],"relation":{},"ISSN":["1613-6810","1613-6829"],"issn-type":[{"value":"1613-6810","type":"print"},{"value":"1613-6829","type":"electronic"}],"subject":[],"published":{"date-parts":[[2026,10,21]]},"assertion":[{"value":"2026-05-29","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2026-10-13","order":2,"name":"accepted","label":"Accepted","group":{"name":"publication_history","label":"Publication History"}},{"value":"2026-10-21","order":3,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}],"article-number":"e76353"}}