{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,14]],"date-time":"2026-10-14T09:06:37Z","timestamp":1791968797044,"version":"4.3.4"},"reference-count":59,"publisher":"Wiley","issue":"1","license":[{"start":{"date-parts":[[2023,11,13]],"date-time":"2023-11-13T00:00:00Z","timestamp":1699833600000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"funder":[{"DOI":"10.13039\/100006151","name":"Basic Energy Sciences","doi-asserted-by":"publisher","award":["Catalysis Science program"],"award-info":[{"award-number":["Catalysis Science program"]}],"id":[{"id":"10.13039\/100006151","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":[[2024,1,2]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Tuning the anionic site of catalyst supports can impact reaction pathways by creating active sites on the support or influencing metal\u2010support interactions when using supported metal nanoparticles. This study focuses on CO<jats:sub>2<\/jats:sub> hydrogenation over supported Cu nanoparticles, revealing a 3\u2010fold increase in methanol yield when replacing oxygen anions with hydrides in the perovskite support (Cu\/BaTiO<jats:sub>2.8<\/jats:sub>H<jats:sub>0.2<\/jats:sub> yields ~146\u2005mg\/h\/gCu vs. Cu\/BaTiO<jats:sub>3<\/jats:sub> yields ~50\u2005mg\/h\/gCu). The contrast suggests that significant roles are played by the support hydrides in the reaction. Temperature programmed reaction and isotopic labelling studies indicate that BaTiO<jats:sub>2.8<\/jats:sub>H<jats:sub>0.2<\/jats:sub> surface hydride species follow a Mars van Krevelen mechanism in CO<jats:sub>2<\/jats:sub> hydrogenation, promoting methanol production. High\u2010pressure steady\u2010state isotopic transient kinetic analysis (SSITKA) studies suggest that Cu\/BaTiO<jats:sub>2.8<\/jats:sub>H<jats:sub>0.2<\/jats:sub> possesses both a higher density and more active and selective sites for methanol production compared to Cu\/BaTiO<jats:sub>3<\/jats:sub>. An operando high\u2010pressure diffuse reflectance infrared spectroscopy (DRIFTS)\u2010SSITKA study shows that formate species are the major surface intermediates over both catalysts, and the subsequent hydrogenation steps of formate are likely rate\u2010limiting. However, the catalytic reactivity of Cu\/BaTiO<jats:sub>2.8<\/jats:sub>H<jats:sub>0.2<\/jats:sub> towards the formate species is much higher than Cu\/BaTiO<jats:sub>3<\/jats:sub>, likely due to the altered electronic structure of interface Cu sites by the hydrides in the support as validated by density functional theory (DFT) calculations.<\/jats:p>","DOI":"10.1002\/anie.202313389","type":"journal-article","created":{"date-parts":[[2023,10,31]],"date-time":"2023-10-31T14:53:55Z","timestamp":1698764035000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":18,"title":["Significant Roles of Surface Hydrides in Enhancing the Performance of Cu\/BaTiO<sub>2.8<\/sub>H<sub>0.2<\/sub> Catalyst for CO<sub>2<\/sub> Hydrogenation to Methanol"],"prefix":"10.1002","volume":"63","author":[{"given":"Yang","family":"He","sequence":"first","affiliation":[{"name":"Chemical Sciences Division and Center for Nanophase Materials Sciences Oak Ridge National Laboratory  Oak Ridge TN-37831 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yuanyuan","family":"Li","sequence":"additional","affiliation":[{"name":"Chemical Sciences Division and Center for Nanophase Materials Sciences Oak Ridge National Laboratory  Oak Ridge TN-37831 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ming","family":"Lei","sequence":"additional","affiliation":[{"name":"Department of Chemical and Biomolecular Engineering Vanderbilt University  Nashville TN-37235 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Felipe","family":"Polo\u2010Garzon","sequence":"additional","affiliation":[{"name":"Chemical Sciences Division and Center for Nanophase Materials Sciences Oak Ridge National Laboratory  Oak Ridge TN-37831 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jorge","family":"Perez\u2010Aguilar","sequence":"additional","affiliation":[{"name":"Stanford Synchrotron Radiation Lightsource SLAC National Accelerator Laboratory  2575 Sand Hill Road Menlo Park CA-94025 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Simon R.","family":"Bare","sequence":"additional","affiliation":[{"name":"Stanford Synchrotron Radiation Lightsource SLAC National Accelerator Laboratory  2575 Sand Hill Road Menlo Park CA-94025 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Eric","family":"Formo","sequence":"additional","affiliation":[{"name":"Georgia Electron Microscopy University of Georgia  Athens GA-30602 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Hwangsun","family":"Kim","sequence":"additional","affiliation":[{"name":"Center for Nanophase Materials Sciences Oak Ridge National Laboratory  Oak Ridge TN-37831 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Luke","family":"Daemen","sequence":"additional","affiliation":[{"name":"Neutron Scattering Division Oak Ridge National Laboratory  Oak Ridge TN-37831 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yongqiang","family":"Cheng","sequence":"additional","affiliation":[{"name":"Neutron Scattering Division Oak Ridge National Laboratory  Oak Ridge TN-37831 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Kunlun","family":"Hong","sequence":"additional","affiliation":[{"name":"Center for Nanophase Materials Sciences Oak Ridge National Laboratory  Oak Ridge TN-37831 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Miaofang","family":"Chi","sequence":"additional","affiliation":[{"name":"Center for Nanophase Materials Sciences Oak Ridge National Laboratory  Oak Ridge TN-37831 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"De\u2010en","family":"Jiang","sequence":"additional","affiliation":[{"name":"Department of Chemical and Biomolecular Engineering Vanderbilt University  Nashville TN-37235 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-4468-3240","authenticated-orcid":false,"given":"Zili","family":"Wu","sequence":"additional","affiliation":[{"name":"Chemical Sciences Division and Center for Nanophase Materials Sciences Oak Ridge National Laboratory  Oak Ridge TN-37831 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2023,11,13]]},"reference":[{"key":"e_1_2_7_1_1","unstructured":"\u00a0"},{"key":"e_1_2_7_2_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.9b00723"},{"key":"e_1_2_7_3_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.jcat.2020.11.039"},{"key":"e_1_2_7_4_2","doi-asserted-by":"publisher","DOI":"10.1038\/nchem.1873"},{"key":"e_1_2_7_5_2","first-page":"230","volume":"1","author":"Zhao H.","year":"2022","journal-title":"Res. Chem. Mater."},{"key":"e_1_2_7_6_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.jcat.2007.04.003"},{"key":"e_1_2_7_7_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201610166"},{"key":"e_1_2_7_8_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.jcat.2010.01.009"},{"key":"e_1_2_7_9_2","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.0c02909"},{"key":"e_1_2_7_10_2","doi-asserted-by":"publisher","DOI":"10.1021\/acssuschemeng.0c07258"},{"key":"e_1_2_7_11_1","unstructured":"\u00a0"},{"key":"e_1_2_7_12_2","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.2c03709"},{"key":"e_1_2_7_13_2","doi-asserted-by":"publisher","DOI":"10.1007\/s12274-022-5092-x"},{"key":"e_1_2_7_14_2","doi-asserted-by":"publisher","DOI":"10.1080\/14686996.2017.1394776"},{"key":"e_1_2_7_15_1","doi-asserted-by":"publisher","DOI":"10.1126\/sciadv.abi6012"},{"key":"e_1_2_7_16_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41929-021-00684-0"},{"key":"e_1_2_7_17_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.matt.2022.06.019"},{"key":"e_1_2_7_18_1","unstructured":"\u00a0"},{"key":"e_1_2_7_19_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr950232u"},{"key":"e_1_2_7_20_2","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.6b02806"},{"key":"e_1_2_7_21_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacsau.1c00542"},{"key":"e_1_2_7_22_2","doi-asserted-by":"publisher","DOI":"10.1039\/D2TA10036C"},{"key":"e_1_2_7_23_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jpclett.2c03391"},{"key":"e_1_2_7_24_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.3c01983"},{"key":"e_1_2_7_25_1","unstructured":"\u00a0"},{"key":"e_1_2_7_26_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.2c00976"},{"key":"e_1_2_7_27_2","doi-asserted-by":"publisher","DOI":"10.1002\/aenm.201801772"},{"key":"e_1_2_7_28_2","doi-asserted-by":"publisher","DOI":"10.1002\/aenm.201800800"},{"key":"e_1_2_7_29_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jpcc.3c00915"},{"key":"e_1_2_7_30_1","doi-asserted-by":"publisher","DOI":"10.1039\/C9TA00086K"},{"key":"e_1_2_7_31_1","doi-asserted-by":"publisher","DOI":"10.1021\/acsomega.8b01368"},{"key":"e_1_2_7_32_1","unstructured":"\u00a0"},{"key":"e_1_2_7_33_2","doi-asserted-by":"publisher","DOI":"10.1038\/s41467-020-16342-1"},{"key":"e_1_2_7_34_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202103087"},{"key":"e_1_2_7_35_1","doi-asserted-by":"publisher","DOI":"10.1007\/s10562-014-1398-y"},{"key":"e_1_2_7_36_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.7b08891"},{"key":"e_1_2_7_37_1","unstructured":"\u00a0"},{"key":"e_1_2_7_38_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jpcc.5b06811"},{"key":"e_1_2_7_39_2","doi-asserted-by":"publisher","DOI":"10.1038\/s41598-021-04640-7"},{"key":"e_1_2_7_40_1","unstructured":"\u00a0"},{"key":"e_1_2_7_41_2","doi-asserted-by":"publisher","DOI":"10.1002\/cssc.202002248"},{"key":"e_1_2_7_42_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.jcat.2009.09.004"},{"key":"e_1_2_7_43_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.cattod.2015.01.011"},{"key":"e_1_2_7_44_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41467-023-36407-1"},{"key":"e_1_2_7_45_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.jcat.2021.12.030"},{"key":"e_1_2_7_46_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.5b01755"},{"key":"e_1_2_7_47_1","unstructured":"\u00a0"},{"key":"e_1_2_7_48_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.6b05791"},{"key":"e_1_2_7_49_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.aal3573"},{"key":"e_1_2_7_50_1","unstructured":"\u00a0"},{"key":"e_1_2_7_51_2","doi-asserted-by":"publisher","DOI":"10.1002\/cctc.202101500"},{"key":"e_1_2_7_52_2","doi-asserted-by":"publisher","DOI":"10.1038\/s41467-020-19634-8"},{"key":"e_1_2_7_53_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.0c07195"},{"key":"e_1_2_7_54_1","unstructured":"\u00a0"},{"key":"e_1_2_7_55_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.cattod.2006.10.003"},{"key":"e_1_2_7_56_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.jcat.2007.09.003"},{"key":"e_1_2_7_57_1","unstructured":"\u00a0"},{"key":"e_1_2_7_58_2","doi-asserted-by":"publisher","DOI":"10.1021\/cs400132a"},{"key":"e_1_2_7_59_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.1219831"}],"container-title":["Angewandte Chemie International Edition"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/am-pdf\/10.1002\/anie.202313389","content-type":"application\/pdf","content-version":"am","intended-application":"syndication"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.202313389","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,1,16]],"date-time":"2025-01-16T15:59:55Z","timestamp":1737043195000},"score":1,"resource":{"primary":{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/10.1002\/anie.202313389"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2023,11,13]]},"references-count":59,"journal-issue":{"issue":"1","published-print":{"date-parts":[[2024,1,2]]}},"alternative-id":["10.1002\/anie.202313389"],"URL":"https:\/\/doi.org\/10.1002\/anie.202313389","archive":["Portico"],"relation":{},"ISSN":["1433-7851","1521-3773"],"issn-type":[{"value":"1433-7851","type":"print"},{"value":"1521-3773","type":"electronic"}],"subject":[],"published":{"date-parts":[[2023,11,13]]},"assertion":[{"value":"2023-09-08","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2023-11-13","order":3,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}],"article-number":"e202313389"}}