{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,21]],"date-time":"2026-09-21T23:50:07Z","timestamp":1790034607013,"version":"4.0.1"},"reference-count":70,"publisher":"American Association for the Advancement of Science (AAAS)","issue":"48","funder":[{"DOI":"10.13039\/501100001809","name":"National Natural Science Foundation of China","doi-asserted-by":"publisher","award":["22203044"],"award-info":[{"award-number":["22203044"]}],"id":[{"id":"10.13039\/501100001809","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100001809","name":"National Natural Science Foundation of China","doi-asserted-by":"publisher","award":["22173048, 22425302"],"award-info":[{"award-number":["22173048, 22425302"]}],"id":[{"id":"10.13039\/501100001809","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100012246","name":"Priority Academic Program Development of Jiangsu Higher Education Institutions","doi-asserted-by":"publisher","id":[{"id":"10.13039\/501100012246","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100012166","name":"National Key R & D Program of China","doi-asserted-by":"crossref","award":["2024YFA1210804, 2024YFA0917802"],"award-info":[{"award-number":["2024YFA1210804, 2024YFA0917802"]}],"id":[{"id":"10.13039\/501100012166","id-type":"DOI","asserted-by":"crossref"}]},{"name":"Jiangsu Specially Appointed Professor Plan"},{"name":"Jiangsu Basic Research Center for Synthetic Biology","award":["BK20233003"],"award-info":[{"award-number":["BK20233003"]}]}],"content-domain":{"domain":["www.science.org"],"crossmark-restriction":true},"short-container-title":["Sci. Adv."],"published-print":{"date-parts":[[2025,11,28]]},"abstract":"<jats:p>\n                    Heterogenized cobalt phthalocyanine (hetero-CoPc) molecular catalysts exhibit domino CO\/methanol selectivity during CO\n                    <jats:sub>2<\/jats:sub>\n                    electroreduction. However, the origin of this selectivity is not well understood, impeding the strategic optimization for methanol generation. Here, we show potential-modulated orbital interaction mechanisms governing the selectivity in hetero-CoPc based on first-principles calculations with consideration of carbon support and electrochemical interfaces. Specifically, constant-potential orbital-resolved analyses reveal that electrons introduced by applied potentials initially occupy the semi-occupied Co-3d\n                    <jats:sub>z<\/jats:sub>\n                    <jats:sub>\n                      <jats:sup>2<\/jats:sup>\n                    <\/jats:sub>\n                    orbital, thus suppressing CO-5\u03c3 \u2192 Co-3d\n                    <jats:sub>z<\/jats:sub>\n                    <jats:sub>\n                      <jats:sup>2<\/jats:sup>\n                    <\/jats:sub>\n                    electron donation. This induces gradual weakening of *CO adsorption while establishing high *CO hydrogenation barriers (restricting the product to CO) over the medium potential range. With further decreasing potentials, a progressive electron population occurs in the Co-3d\n                    <jats:sub>yz<\/jats:sub>\n                    \/d\n                    <jats:sub>xz<\/jats:sub>\n                    orbitals, promoting the Co-3d\n                    <jats:sub>xz<\/jats:sub>\n                    \/d\n                    <jats:sub>yz<\/jats:sub>\n                    \u2192 CO-2\u03c0* back-donation. This facilitates the activation of the C\u2500O bond of *CO, thereby reducing its hydrogenation barriers and enabling methanol production at more negative potentials. Similar analyses also rationalize experimental observations for other heterogenized metal phthalocyanines, showing the importance of potential-modulated orbital interactions for selectivity engineering.\n                  <\/jats:p>","DOI":"10.1126\/sciadv.adz9944","type":"journal-article","created":{"date-parts":[[2025,11,26]],"date-time":"2025-11-26T19:01:51Z","timestamp":1764183711000},"update-policy":"https:\/\/doi.org\/10.34133\/aaas_crossmark","source":"Crossref","is-referenced-by-count":8,"title":["Potential-modulated orbital interactions determine domino CO\/methanol selectivity for CO\n                    <sub>2<\/sub>\n                    electroreduction on cobalt phthalocyanine"],"prefix":"10.1126","volume":"11","author":[{"ORCID":"https:\/\/orcid.org\/0009-0008-9594-005X","authenticated-orcid":true,"given":"Juan","family":"Zhang","sequence":"first","affiliation":[{"name":"State Key Laboratory of Microbial Technology, Jiangsu Key Laboratory of New Power Batteries, School of Chemistry and Materials Science, Nanjing Normal University, Nanjing 210023, China."}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8833-9564","authenticated-orcid":true,"given":"Yu","family":"Wang","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Microbial Technology, Jiangsu Key Laboratory of New Power Batteries, School of Chemistry and Materials Science, Nanjing Normal University, Nanjing 210023, China."}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-6136-863X","authenticated-orcid":true,"given":"Yafei","family":"Li","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Microbial Technology, Jiangsu Key Laboratory of New Power Batteries, School of Chemistry and Materials Science, Nanjing Normal University, Nanjing 210023, China."}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"221","reference":[{"key":"e_1_3_2_2_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.aav3506"},{"key":"e_1_3_2_3_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2023.215081"},{"key":"e_1_3_2_4_2","doi-asserted-by":"publisher","DOI":"10.1038\/s41570-021-00289-y"},{"key":"e_1_3_2_5_2","doi-asserted-by":"publisher","DOI":"10.1038\/s41560-019-0450-y"},{"key":"e_1_3_2_6_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.nantod.2018.05.001"},{"key":"e_1_3_2_7_2","doi-asserted-by":"publisher","DOI":"10.1002\/adma.202001848"},{"key":"e_1_3_2_8_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.esci.2023.100140"},{"key":"e_1_3_2_9_2","doi-asserted-by":"publisher","DOI":"10.1038\/s41467-017-01035-z"},{"key":"e_1_3_2_10_2","doi-asserted-by":"publisher","DOI":"10.1038\/s41467-025-57464-8"},{"key":"e_1_3_2_11_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacsau.3c00026"},{"key":"e_1_3_2_12_2","doi-asserted-by":"publisher","DOI":"10.1039\/D2SC01593E"},{"key":"e_1_3_2_13_2","doi-asserted-by":"publisher","DOI":"10.1039\/c39740000158"},{"key":"e_1_3_2_14_2","doi-asserted-by":"publisher","DOI":"10.1007\/BF01023606"},{"key":"e_1_3_2_15_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.2c07178"},{"key":"e_1_3_2_16_2","doi-asserted-by":"publisher","DOI":"10.1038\/s41560-020-0666-x"},{"key":"e_1_3_2_17_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.4c05669"},{"key":"e_1_3_2_18_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.accounts.1c00200"},{"key":"e_1_3_2_19_2","doi-asserted-by":"publisher","DOI":"10.1039\/D0CS01605E"},{"key":"e_1_3_2_20_2","doi-asserted-by":"publisher","DOI":"10.1038\/ncomms14675"},{"key":"e_1_3_2_21_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.checat.2024.101014"},{"key":"e_1_3_2_22_2","doi-asserted-by":"publisher","DOI":"10.1002\/advs.202501459"},{"key":"e_1_3_2_23_2","doi-asserted-by":"publisher","DOI":"10.1038\/s41560-020-0667-9"},{"key":"e_1_3_2_24_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202420286"},{"key":"e_1_3_2_25_2","doi-asserted-by":"publisher","DOI":"10.1038\/s41586-019-1760-8"},{"key":"e_1_3_2_26_2","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.3c05089"},{"key":"e_1_3_2_27_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.4c14409"},{"key":"e_1_3_2_28_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.2c06953"},{"key":"e_1_3_2_29_2","doi-asserted-by":"publisher","DOI":"10.1038\/s41929-021-00705-y"},{"key":"e_1_3_2_30_2","doi-asserted-by":"publisher","DOI":"10.1038\/s41467-024-52168-x"},{"key":"e_1_3_2_31_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jpclett.4c02755"},{"key":"e_1_3_2_32_2","doi-asserted-by":"publisher","DOI":"10.1039\/D4CY00214H"},{"key":"e_1_3_2_33_2","doi-asserted-by":"publisher","DOI":"10.1038\/s41929-024-01190-9"},{"key":"e_1_3_2_34_2","doi-asserted-by":"publisher","DOI":"10.1038\/s41929-024-01197-2"},{"key":"e_1_3_2_35_2","doi-asserted-by":"publisher","DOI":"10.1039\/D1SC04094D"},{"key":"e_1_3_2_36_2","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.2c05540"},{"key":"e_1_3_2_37_2","doi-asserted-by":"publisher","DOI":"10.1021\/jz201461p"},{"key":"e_1_3_2_38_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jpclett.4c01032"},{"key":"e_1_3_2_39_2","doi-asserted-by":"publisher","DOI":"10.1038\/s42004-025-01579-y"},{"key":"e_1_3_2_40_2","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.3c04957"},{"key":"e_1_3_2_41_2","doi-asserted-by":"publisher","DOI":"10.1038\/s41467-023-39153-6"},{"key":"e_1_3_2_42_2","doi-asserted-by":"publisher","DOI":"10.1021\/acsaem.3c02979"},{"key":"e_1_3_2_43_2","doi-asserted-by":"publisher","DOI":"10.1038\/s41565-025-01866-8"},{"key":"e_1_3_2_44_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.5c02411"},{"key":"e_1_3_2_45_2","doi-asserted-by":"publisher","DOI":"10.1039\/c0ee00071j"},{"key":"e_1_3_2_46_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202310623"},{"key":"e_1_3_2_47_2","doi-asserted-by":"publisher","DOI":"10.1016\/0927-0256(96)00008-0"},{"key":"e_1_3_2_48_2","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevB.59.7413"},{"key":"e_1_3_2_49_2","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevB.50.17953"},{"key":"e_1_3_2_50_2","doi-asserted-by":"publisher","DOI":"10.1002\/jcc.21759"},{"key":"e_1_3_2_51_2","doi-asserted-by":"publisher","DOI":"10.1002\/jcc.24300"},{"key":"e_1_3_2_52_2","doi-asserted-by":"publisher","DOI":"10.1002\/jcc.26353"},{"key":"e_1_3_2_53_2","doi-asserted-by":"publisher","DOI":"10.1039\/C7RA11829E"},{"key":"e_1_3_2_54_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.4c05444"},{"key":"e_1_3_2_55_2","doi-asserted-by":"publisher","DOI":"10.1038\/s44160-023-00384-6"},{"key":"e_1_3_2_56_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.4865107"},{"key":"e_1_3_2_57_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.5132354"},{"key":"e_1_3_2_58_2","doi-asserted-by":"publisher","DOI":"10.1038\/s41467-020-16119-6"},{"key":"e_1_3_2_59_2","doi-asserte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