{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,11,7]],"date-time":"2026-11-07T04:50:19Z","timestamp":1794027019115,"version":"4.8.0"},"reference-count":38,"publisher":"Springer Science and Business Media LLC","issue":"1","license":[{"start":{"date-parts":[[2024,6,1]],"date-time":"2024-06-01T00:00:00Z","timestamp":1717200000000},"content-version":"tdm","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0"},{"start":{"date-parts":[[2024,6,1]],"date-time":"2024-06-01T00:00:00Z","timestamp":1717200000000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0"}],"funder":[{"name":"the Strategic Priority Research Program of Chinese Academy of Sciences"}],"content-domain":{"domain":["link.springer.com"],"crossmark-restriction":false},"short-container-title":["Nat Commun"],"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>\n                    Tungsten trioxide (WO\n                    <jats:sub>3<\/jats:sub>\n                    ) has been recognized as the most promising photocatalyst for highly selective oxidation of methane (CH\n                    <jats:sub>4<\/jats:sub>\n                    ) to formaldehyde (HCHO), but the origin of catalytic activity and the reaction manner remain controversial. Here, we take {001} and {110} facets dominated WO\n                    <jats:sub>3<\/jats:sub>\n                    as the model photocatalysts. Distinctly, {001} facet can readily achieve 100% selectivity of HCHO via the active site mechanism whereas {110} facet hardly guarantees a high selectivity of HCHO along with many intermediate products via the radical way. In situ diffuse reflectance infrared Fourier transform spectroscopy, electron paramagnetic resonance and theoretical calculations confirm that the competitive chemical adsorption between CH\n                    <jats:sub>4<\/jats:sub>\n                    and H\n                    <jats:sub>2<\/jats:sub>\n                    O and the different CH\n                    <jats:sub>4<\/jats:sub>\n                    activation routes on WO\n                    <jats:sub>3<\/jats:sub>\n                    surface are responsible for diverse CH\n                    <jats:sub>4<\/jats:sub>\n                    oxidation pathways. The microscopic mechanism elucidation provides the guidance for designing high performance photocatalysts for selective CH\n                    <jats:sub>4<\/jats:sub>\n                    oxidation.\n                  <\/jats:p>","DOI":"10.1038\/s41467-024-49138-8","type":"journal-article","created":{"date-parts":[[2024,6,1]],"date-time":"2024-06-01T06:01:28Z","timestamp":1717221688000},"update-policy":"https:\/\/doi.org\/10.1007\/springer_crossmark_policy","source":"Crossref","is-referenced-by-count":110,"title":["Insight into selectivity of photocatalytic methane oxidation to formaldehyde on tungsten trioxide"],"prefix":"10.1038","volume":"15","author":[{"given":"Yingying","family":"Fan","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7160-0025","authenticated-orcid":false,"given":"Yuheng","family":"Jiang","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Haiting","family":"Lin","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jianan","family":"Li","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yuanjiang","family":"Xie","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Anyi","family":"Chen","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Siyang","family":"Li","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7343-2221","authenticated-orcid":false,"given":"Dongxue","family":"Han","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3652-2903","authenticated-orcid":false,"given":"Li","family":"Niu","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-0610-0064","authenticated-orcid":false,"given":"Zhiyong","family":"Tang","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"297","published-online":{"date-parts":[[2024,6,1]]},"reference":[{"key":"49138_CR1","doi-asserted-by":"publisher","first-page":"740","DOI":"10.1021\/jacs.1c09141","volume":"144","author":"L Luo","year":"2022","unstructured":"Luo, L. et al. Binary Au\u2013Cu reaction sites decorated ZnO for selective methane oxidation to c1 oxygenates with nearly 100% selectivity at room temperature. J. Am. Chem. Soc. 144, 740\u2013750 (2022).","journal-title":"J. Am. Chem. Soc."},{"key":"49138_CR2","doi-asserted-by":"publisher","first-page":"1032","DOI":"10.1038\/s41929-021-00708-9","volume":"4","author":"S Song","year":"2021","unstructured":"Song, S. et al. A selective Au-ZnO\/TiO2 hybrid photocatalyst for oxidative coupling of methane to ethane with dioxygen. Nat. Catal. 4, 1032\u20131042 (2021).","journal-title":"Nat. Catal."},{"key":"49138_CR3","doi-asserted-by":"publisher","first-page":"509","DOI":"10.1038\/s41893-021-00682-x","volume":"4","author":"Y Fan","year":"2021","unstructured":"Fan, Y. et al. Selective photocatalytic oxidation of methane by quantum-sized bismuth vanadate. Nat. Sustain. 4, 509\u2013515 (2021).","journal-title":"Nat. Sustain."},{"key":"49138_CR4","doi-asserted-by":"publisher","DOI":"10.1038\/s41467-022-30434-0","volume":"13","author":"L Luo","year":"2022","unstructured":"Luo, L. et al. Synergy of Pd atoms and oxygen vacancies on In2O3 for methane conversion under visible light. Nat. Commun. 13, 2930 (2022).","journal-title":"Nat. Commun."},{"key":"49138_CR5","doi-asserted-by":"publisher","DOI":"10.1038\/s41467-021-24912-0","volume":"12","author":"N Feng","year":"2021","unstructured":"Feng, N. et al. Efficient and selective photocatalytic CH4 conversion to CH3OH with O2 by controlling overoxidation on TiO2. Nat. Commun. 12, 4652 (2021).","journal-title":"Nat. Commun."},{"key":"49138_CR6","doi-asserted-by":"publisher","first-page":"14318","DOI":"10.1021\/acscatal.0c04329","volume":"10","author":"H Song","year":"2020","unstructured":"Song, H. et al. Selective photo-oxidation of methane to methanol with oxygen over dual-cocatalyst-modified titanium dioxide. ACS Catal 10, 14318\u201314326 (2020).","journal-title":"ACS Catal"},{"key":"49138_CR7","doi-asserted-by":"publisher","first-page":"20507","DOI":"10.1021\/jacs.9b11440","volume":"141","author":"H Song","year":"2019","unstructured":"Song, H. et al. Direct and selective photocatalytic oxidation of CH4 to oxygenates with O2 on Cocatalysts\/ZnO at room temperature in water. J. Am. Chem. Soc. 141, 20507\u201320515 (2019).","journal-title":"J. Am. Chem. Soc."},{"key":"49138_CR8","doi-asserted-by":"publisher","first-page":"120919","DOI":"10.1016\/j.apcatb.2021.120919","volume":"306","author":"Y Zeng","year":"2022","unstructured":"Zeng, Y. et al. Photocatalytic oxidation of methane to methanol by tungsten trioxide-supported atomic gold at room temperature. Appl. Catal. B: Environ. 306, 120919 (2022).","journal-title":"Appl. Catal. B: Environ."},{"key":"49138_CR9","doi-asserted-by":"publisher","first-page":"119661","DOI":"10.1016\/j.apcatb.2020.119661","volume":"283","author":"S Wei","year":"2021","unstructured":"Wei, S. et al. Aerobic oxidation of methane to formaldehyde mediated by crystal-O over gold modified tungsten trioxide via photocatalysis. Appl. Catal. B: Environ. 283, 119661 (2021).","journal-title":"Appl. Catal. B: Environ."},{"key":"49138_CR10","doi-asserted-by":"publisher","first-page":"106365","DOI":"10.1016\/j.catcom.2021.106365","volume":"161","author":"Y Fan","year":"2021","unstructured":"Fan, Y. et al. Highly selective oxidation of methane to formaldehyde on tungsten trioxide by lattice oxygen. Catal. Commun. 161, 106365 (2021).","journal-title":"Catal. Commun."},{"key":"49138_CR11","doi-asserted-by":"publisher","first-page":"30","DOI":"10.1016\/j.apcatb.2016.01.032","volume":"187","author":"K Villa","year":"2016","unstructured":"Villa, K., Murcia-Lopez, S., Ramon, J. & Andreu, T. An insight on the role of La in mesoporous WO3 for the photocatalytic conversion of methane into methanol. Appl. Catal. B: Environ. 187, 30\u201336 (2016).","journal-title":"Appl. Catal. B: Environ."},{"key":"49138_CR12","doi-asserted-by":"publisher","first-page":"150","DOI":"10.1016\/j.apcatb.2014.07.055","volume":"163","author":"K Villa","year":"2015","unstructured":"Villa, K., Murcia-Lopez, S., Andreu, T. & Ramon, J. Mesoporous WO3 photocatalyst for the partial oxidation of methane to methanol using electron scavengers. Appl. Catal. B: Environ. 163, 150\u2013155 (2015).","journal-title":"Appl. Catal. B: Environ."},{"key":"49138_CR13","doi-asserted-by":"publisher","first-page":"200","DOI":"10.1016\/j.catcom.2014.09.025","volume":"58","author":"K Villa","year":"2015","unstructured":"Villa, K., Murcia-Lopez, S., Andreu, T. & Morante, J. R. On the role of WO3 surface hydroxyl groups for the photocatalytic partial oxidation of methane to methanol. Catal. Commun. 58, 200\u2013203 (2015).","journal-title":"Catal. Commun."},{"key":"49138_CR14","doi-asserted-by":"publisher","first-page":"327","DOI":"10.1016\/j.apcata.2013.10.045","volume":"470","author":"A Hameed","year":"2014","unstructured":"Hameed, A., Ismail, I., Aslam, M. & Gondal, M. A. Photocatalytic conversion of methane into methanol: Performance of silver impregnated WO3. Appl. Catal. A: General 470, 327\u2013335 (2014).","journal-title":"Appl. Catal. A: General"},{"key":"49138_CR15","doi-asserted-by":"publisher","first-page":"7459","DOI":"10.1021\/acs.jpclett.1c02053","volume":"12","author":"Y Zhu","year":"2021","unstructured":"Zhu, Y. et al. Distinct pathways in visible-light driven thermo-photo catalytic methane conversion. J. Phys. Chem. Lett. 12, 7459\u20137465 (2021).","journal-title":"J. Phys. Chem. Lett."},{"key":"49138_CR16","doi-asserted-by":"publisher","DOI":"10.1038\/s41467-022-30532-z","volume":"13","author":"W Zhang","year":"2022","unstructured":"Zhang, W. et al. High-performance photocatalytic nonoxidative conversion of methane to ethane and hydrogen by heteroatoms-engineered TiO2. Nat. Commun. 13, 2806 (2022).","journal-title":"Nat. Commun."},{"key":"49138_CR17","doi-asserted-by":"publisher","first-page":"1587","DOI":"10.1021\/la010970f","volume":"18","author":"J Senkevich","year":"2002","unstructured":"Senkevich, J., Mitchell, C., Yang, G. & Lu, T. Surface chemistry of mercaptan and growth of pyridine short-chain alkoxy silane molecular layers. Langmuir 18, 1587\u20131594 (2002).","journal-title":"Langmuir"},{"key":"49138_CR18","doi-asserted-by":"publisher","first-page":"12273","DOI":"10.1038\/ncomms12273","volume":"7","author":"X Chen","year":"2016","unstructured":"Chen, X. et al. Photocatalytic oxidation of methane over silver decorated zinc oxide nanocatalysts. Nat. Commun. 7, 12273\u201312280 (2016).","journal-title":"Nat. Commun."},{"key":"49138_CR19","doi-asserted-by":"publisher","first-page":"111","DOI":"10.1016\/j.apcatb.2011.03.041","volume":"105","author":"B Hauchecorne","year":"2011","unstructured":"Hauchecorne, B. et al. Photocatalytic degradation of ethylene: An FTIR in situ study under atmospheric conditions. Appl. Catal. B: Environ. 105, 111\u2013116 (2011).","journal-title":"Appl. Catal. B: Environ."},{"key":"49138_CR20","doi-asserted-by":"publisher","first-page":"6508","DOI":"10.1021\/ja211638e","volume":"134","author":"G Xi","year":"2012","unstructured":"Xi, G. et al. In situ growth of metal particles on 3D Urchin-like WO3 nanostructures. J. Am. Chem. Soc. 134, 6508\u20136511 (2012).","journal-title":"J. Am. Chem. Soc."},{"key":"49138_CR21","doi-asserted-by":"publisher","first-page":"325","DOI":"10.1016\/j.materresbull.2013.08.028","volume":"49","author":"S Adhikari","year":"2014","unstructured":"Adhikari, S., Sarkar, D. & Maiti, H. Synthesis and characterization of WO3 spherical nanoparticles and nanorods. Mater. Res. Bull. 49, 325\u2013330 (2014).","journal-title":"Mater. Res. Bull."},{"key":"49138_CR22","doi-asserted-by":"publisher","first-page":"1154","DOI":"10.1016\/j.apsusc.2019.03.094","volume":"481","author":"R Wu","year":"2019","unstructured":"Wu, R. et al. CH4 activation and sensing on hexagonal WO3 (001) and (110) surfaces. Appl. Surf. Sci. 481, 1154\u20131159 (2019).","journal-title":"Appl. Surf. Sci."},{"key":"49138_CR23","doi-asserted-by":"publisher","first-page":"11302","DOI":"10.1021\/acs.chemrev.7b00161","volume":"117","author":"Y Nosaka","year":"2017","unstructured":"Nosaka, Y. & Nosaka, A. Generation and detection of reactive oxygen species in photocatalysis. Chem. Rev. 117, 11302\u201311336 (2017).","journal-title":"Chem. Rev."},{"key":"49138_CR24","doi-asserted-by":"publisher","first-page":"9978","DOI":"10.1021\/ja211919k","volume":"134","author":"S Tan","year":"2012","unstructured":"Tan, S. et al. Observation of photocatalytic dissociation of water on terminal Ti sites of TiO2(110)-1 \u00d7 1 surface. J. Am. Chem. Soc. 134, 9978\u20139985 (2012).","journal-title":"J. Am. Chem. Soc."},{"key":"49138_CR25","doi-asserted-by":"publisher","first-page":"41","DOI":"10.1016\/j.progsurf.2010.10.002","volume":"86","author":"P Salvador","year":"2011","unstructured":"Salvador, P. Mechanisms of water photooxidation at n-TiO2 rutile single crystal oriented electrodes under UV illumination in competition with photocorrosion. Prog. Surf. Sci. 86, 41\u201358 (2011).","journal-title":"Prog. Surf. Sci."},{"key":"49138_CR26","doi-asserted-by":"publisher","first-page":"10083","DOI":"10.1021\/jp500315u","volume":"118","author":"V Diesen","year":"2014","unstructured":"Diesen, V. & Jonsson, M. Formation of H2O2 in TiO2 photocatalysis of oxygenated and deoxygenated aqueous systems: A probe for photocatalytically produced hydroxyl radicals. J. Phys. Chem. C 118, 10083\u201310087 (2014).","journal-title":"J. Phys. Chem. C"},{"key":"49138_CR27","doi-asserted-by":"publisher","first-page":"218","DOI":"10.1016\/j.commatsci.2012.10.022","volume":"68","author":"X Wang","year":"2013","unstructured":"Wang, X. et al. Surface stabilization of hexagonal WO3 by non-metallic atoms: A DFT study. Comp. Mater. Sci. 68, 218\u2013221 (2013).","journal-title":"Comp. Mater. Sci."},{"key":"49138_CR28","doi-asserted-by":"publisher","first-page":"996","DOI":"10.1002\/cphc.201201048","volume":"14","author":"L Liu","year":"2013","unstructured":"Liu, L., Wang, Z., Pan, C., Xiao, W. & Cho, K. Effect of hydrogen on O2 adsorption and dissociation on a TiO2 anatase (001) surface. ChemPhysChem. 14, 996\u20131002 (2013).","journal-title":"ChemPhysChem."},{"key":"49138_CR29","doi-asserted-by":"publisher","first-page":"4872","DOI":"10.1002\/anie.202012306","volume":"60","author":"W Zhang","year":"2021","unstructured":"Zhang, W. et al. Hot-electron-induced photothermal catalysis for energy-dependent molecular oxygen activation. Angew. Chem. Int. Ed. 60, 4872\u20134878 (2021).","journal-title":"Angew. Chem. Int. Ed."},{"key":"49138_CR30","doi-asserted-by":"publisher","first-page":"223","DOI":"10.1126\/science.aan6515","volume":"358","author":"N Agarwal","year":"2017","unstructured":"Agarwal, N. et al. Aqueous Au-Pd colloids catalyze selective CH4 oxidation to CH3OH with O2 under mild conditions. Science 358, 223\u2013227 (2017).","journal-title":"Science"},{"key":"49138_CR31","doi-asserted-by":"publisher","first-page":"2698","DOI":"10.1021\/jacs.2c13313","volume":"145","author":"Y Jiang","year":"2023","unstructured":"Jiang, Y. et al. Enabling specific photocatalytic methane oxidation by controlling free radical type. J. Am. Chem. Soc. 145, 2698\u20132707 (2023).","journal-title":"J. Am. Chem. Soc."},{"key":"49138_CR32","doi-asserted-by":"publisher","first-page":"10367","DOI":"10.1021\/acsami.6b02275","volume":"8","author":"N Zhang","year":"2016","unstructured":"Zhang, N. et al. Monoclinic tungsten oxide with {100} facet orientation and tuned electronic band structure for enhanced photocatalytic oxidations. ACS Appl. Mater. Interfaces 8, 10367\u201310374 (2016).","journal-title":"ACS Appl. Mater. Interfaces"},{"key":"49138_CR33","doi-asserted-by":"publisher","first-page":"23212","DOI":"10.1021\/acsami.7b06139","volume":"9","author":"E Albanese","year":"2017","unstructured":"Albanese, E., Di, C. & Pacchioni, G. H2O adsorption on WO3 and WO3\u2013x (001) surfaces. ACS Appl. Mater. Interfaces 9, 23212\u201323221 (2017).","journal-title":"ACS Appl. Mater. Interfaces"},{"key":"49138_CR34","doi-asserted-by":"publisher","first-page":"11770","DOI":"10.1021\/nn5053684","volume":"8","author":"W Li","year":"2014","unstructured":"Li, W. et al. WO3 nanoflakes for enhanced photoelectrochemical conversion. ACS Nano 8, 11770\u201311777 (2014).","journal-title":"ACS Nano"},{"key":"49138_CR35","doi-asserted-by":"publisher","DOI":"10.1038\/s41467-018-07774-x","volume":"10","author":"J Besnardiere","year":"2019","unstructured":"Besnardiere, J. et al. Structure and electrochromism of two-dimensional octahedral molecular sieve h\u2019-WO3. Nat. Commun. 10, 327 (2019).","journal-title":"Nat. Commun."},{"key":"49138_CR36","doi-asserted-by":"publisher","first-page":"18318","DOI":"10.1021\/ja3067622","volume":"134","author":"Q Mi","year":"2012","unstructured":"Mi, Q. et al. Thermally stable N2-intercalated WO3 photoanodes for water oxidation. J. Am. Chem. Soc. 134, 18318\u201318324 (2012).","journal-title":"J. Am. Chem. Soc."},{"key":"49138_CR37","doi-asserted-by":"publisher","DOI":"10.1038\/s41467-023-38334-7","volume":"14","author":"L Luo","year":"2023","unstructured":"Luo, L. et al. Nearly 100% selective and visible-light-driven methane conversion to formaldehyde via. single-atom Cu and W\u03b4+. Nat. Commun. 14, 2690 (2023).","journal-title":"Nat. Commun."},{"key":"49138_CR38","doi-asserted-by":"publisher","first-page":"13277","DOI":"10.1039\/D0TA02793F","volume":"8","author":"W Zhou","year":"2020","unstructured":"Zhou, W. et al. Highly selective aerobic oxidation of methane to methanol over gold decorated zinc oxide via photocatalysis. J. Mater. Chem. A 8, 13277\u201313284 (2020).","journal-title":"J. Mater. Chem. A"}],"container-title":["Nature Communications"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.nature.com\/articles\/s41467-024-49138-8.pdf","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/www.nature.com\/articles\/s41467-024-49138-8","content-type":"text\/html","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/www.nature.com\/articles\/s41467-024-49138-8.pdf","content-type":"application\/pdf","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2024,11,7]],"date-time":"2024-11-07T17:01:57Z","timestamp":1730998917000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.nature.com\/articles\/s41467-024-49138-8"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2024,6,1]]},"references-count":38,"journal-issue":{"issue":"1","published-online":{"date-parts":[[2024,12]]}},"alternative-id":["49138"],"URL":"https:\/\/doi.org\/10.1038\/s41467-024-49138-8","relation":{},"ISSN":["2041-1723"],"issn-type":[{"value":"2041-1723","type":"electronic"}],"subject":[],"published":{"date-parts":[[2024,6,1]]},"assertion":[{"value":"9 October 2022","order":1,"name":"received","label":"Received","group":{"name":"ArticleHistory","label":"Article History"}},{"value":"21 May 2024","order":2,"name":"accepted","label":"Accepted","group":{"name":"ArticleHistory","label":"Article History"}},{"value":"1 June 2024","order":3,"name":"first_online","label":"First Online","group":{"name":"ArticleHistory","label":"Article History"}},{"value":"The authors declare no competing interests.","order":1,"name":"Ethics","group":{"name":"EthicsHeading","label":"Competing interests"}}],"article-number":"4679"}}