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However, thermodynamic parallels between HCHO and methanol (CH3OH) formation limit product selectivity. Using titanium dioxide (TiO2), we have engineered symmetry-breaking sites to overcome this constraint. The studies reveal that symmetry-breaking sites generate surface hole-trapping states, enabling rapid hole migration (\u223c8 ps). This process combines with adsorbed hydroxyl groups to produce hydroxyl radicals (\u2022OH), which cleave titanium\u2013oxygen (Ti\u2013O) bonds in methoxy intermediates. The resulting methoxy radicals (\u2022OCH3) drive a single-step pathway that entirely bypasses CH3OH formation, achieving 93.7% HCHO selectivity with HCHO accounting for 100% of liquid products. In sharp contrast, symmetric sites follow a two-step pathway involving substantial CH3OH coproduction via slower electron transfer (&amp;gt;4 ns), yielding only \u223c42.8% HCHO selectivity. This work demonstrates a breakthrough in sustainable HCHO production, with symmetry-breaking site engineering commandeering photoinduced charge dynamics to eliminate selectivity barriers.<\/jats:p>","DOI":"10.1021\/jacs.6c06804","type":"journal-article","created":{"date-parts":[[2026,6,16]],"date-time":"2026-06-16T09:24:33Z","timestamp":1781601873000},"page":"34219-34230","source":"Crossref","is-referenced-by-count":2,"title":["Highly\nSelective Methane Photooxidation to Formaldehyde\nby Constructing Symmetry-Breaking Sites"],"prefix":"10.1021","volume":"148","author":[{"given":"Yuehan","family":"Cao","sequence":"first","affiliation":[{"name":"Southwest Petroleum University , , ,","place":["Chengdu, China, 610500"]},{"name":"Southwest Petroleum University , , ,","place":["Chengdu, China, 610500"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Chuan","family":"Huang","sequence":"additional","affiliation":[{"name":"Southwest Petroleum University , , ,","place":["Chengdu, China, 610500"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yi","family":"Li","sequence":"additional","affiliation":[{"name":"Southwest Petroleum University , , ,","place":["Chengdu, China, 610500"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Kaibo","family":"Zheng","sequence":"additional","affiliation":[{"name":"Lund University , , P.O. Box 124, ,","place":["Lund, Sweden, 22100"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jie","family":"Qiu","sequence":"additional","affiliation":[{"name":"Southwest Petroleum University , , ,","place":["Chengdu, China, 610500"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yingjie","family":"Shuai","sequence":"additional","affiliation":[{"name":"Southwest Petroleum University , , ,","place":["Chengdu, China, 610500"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9995-0652","authenticated-orcid":true,"given":"Ying","family":"Zhou","sequence":"additional","affiliation":[{"name":"Southwest Petroleum University , , ,","place":["Chengdu, China, 610500"]},{"name":"Southwest Petroleum University , , ,","place":["Chengdu, China, 610500"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,6,16]]},"reference":[{"issue":"13","key":"2026081910231780100_cit1","doi-asserted-by":"publisher","first-page":"8497","DOI":"10.1021\/acs.chemrev.6b00715","article-title":"Direct conversion of methane to value-added chemicals\nover heterogeneous catalysts: challenges and prospects","volume":"117","author":"Schwach","year":"2017","journal-title":"Chem. 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