{"title":"选择性光驱动甲烷氧化制乙醇","authors":"Fei Xue, Chunyang Zhang, Cheng Cheng, Xueli Yan, Feng Liu, Xiaozhi Liu, Biao Jiang, Qiuyue Zhang, Lin Sun, Huiping Peng, Wei-Hsiang Huang, Chih-Wen Pao, Zhiwei Hu, Mingshu Chen, Dong Su, Maochang Liu, Xiaoqing Huang, Yong Xu","doi":"10.1038/s41467-024-54835-5","DOIUrl":null,"url":null,"abstract":"<p>Methane (CH<sub>4</sub>) photocatalytic upgrading to value-added chemicals, especially C<sub>2</sub> products, is significant yet challenging due to sluggish energy/mass transfer and insufficient chemical driven-force in single photochemical process. Herein, we realize solar-driven CH<sub>4</sub> oxidation to ethanol (C<sub>2</sub>H<sub>5</sub>OH) on crystalline carbon nitride (CCN) modified with Cu<sub>9</sub>S<sub>5</sub> and Cu single atoms (Cu<sub>9</sub>S<sub>5</sub>/Cu-CCN). The integration of photothermal effect and photocatalysis overcomes CH<sub>4</sub>-to-C<sub>2</sub>H<sub>5</sub>OH conversion bottlenecks, with Cu<sub>9</sub>S<sub>5</sub> as a hotspot to convert solar-energy to heat. In-situ characterizations demonstrate that Cu single atoms play as electron acceptor for O<sub>2</sub> reduction to ·OOH/ · OH, while Cu<sub>9</sub>S<sub>5</sub> acts as hole acceptor and site for CH<sub>4</sub> adsorption, C − H activation, and C − C coupling. Theoretical calculations demonstrate that Cu<sub>9</sub>S<sub>5</sub>/Cu-CCN reduces C − C coupling energy barrier by stabilizing ·CH<sub>3</sub> and ·CH<sub>2</sub>O. Impressively, C<sub>2</sub>H<sub>5</sub>OH productivity reaches 549.7 μmol g<sup>–1</sup> h<sup>–1</sup>, with selectivity of 94.8% and apparent quantum efficiency of 0.9% (420 nm). This work provides a sustainable avenue for CH<sub>4</sub> conversion to value-added chemcials.</p>","PeriodicalId":19066,"journal":{"name":"Nature Communications","volume":"77 1","pages":""},"PeriodicalIF":14.7000,"publicationDate":"2024-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Selective light-driven methane oxidation to ethanol\",\"authors\":\"Fei Xue, Chunyang Zhang, Cheng Cheng, Xueli Yan, Feng Liu, Xiaozhi Liu, Biao Jiang, Qiuyue Zhang, Lin Sun, Huiping Peng, Wei-Hsiang Huang, Chih-Wen Pao, Zhiwei Hu, Mingshu Chen, Dong Su, Maochang Liu, Xiaoqing Huang, Yong Xu\",\"doi\":\"10.1038/s41467-024-54835-5\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>Methane (CH<sub>4</sub>) photocatalytic upgrading to value-added chemicals, especially C<sub>2</sub> products, is significant yet challenging due to sluggish energy/mass transfer and insufficient chemical driven-force in single photochemical process. Herein, we realize solar-driven CH<sub>4</sub> oxidation to ethanol (C<sub>2</sub>H<sub>5</sub>OH) on crystalline carbon nitride (CCN) modified with Cu<sub>9</sub>S<sub>5</sub> and Cu single atoms (Cu<sub>9</sub>S<sub>5</sub>/Cu-CCN). The integration of photothermal effect and photocatalysis overcomes CH<sub>4</sub>-to-C<sub>2</sub>H<sub>5</sub>OH conversion bottlenecks, with Cu<sub>9</sub>S<sub>5</sub> as a hotspot to convert solar-energy to heat. In-situ characterizations demonstrate that Cu single atoms play as electron acceptor for O<sub>2</sub> reduction to ·OOH/ · OH, while Cu<sub>9</sub>S<sub>5</sub> acts as hole acceptor and site for CH<sub>4</sub> adsorption, C − H activation, and C − C coupling. Theoretical calculations demonstrate that Cu<sub>9</sub>S<sub>5</sub>/Cu-CCN reduces C − C coupling energy barrier by stabilizing ·CH<sub>3</sub> and ·CH<sub>2</sub>O. Impressively, C<sub>2</sub>H<sub>5</sub>OH productivity reaches 549.7 μmol g<sup>–1</sup> h<sup>–1</sup>, with selectivity of 94.8% and apparent quantum efficiency of 0.9% (420 nm). This work provides a sustainable avenue for CH<sub>4</sub> conversion to value-added chemcials.</p>\",\"PeriodicalId\":19066,\"journal\":{\"name\":\"Nature Communications\",\"volume\":\"77 1\",\"pages\":\"\"},\"PeriodicalIF\":14.7000,\"publicationDate\":\"2024-12-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Nature Communications\",\"FirstCategoryId\":\"103\",\"ListUrlMain\":\"https://doi.org/10.1038/s41467-024-54835-5\",\"RegionNum\":1,\"RegionCategory\":\"综合性期刊\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"MULTIDISCIPLINARY SCIENCES\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Nature Communications","FirstCategoryId":"103","ListUrlMain":"https://doi.org/10.1038/s41467-024-54835-5","RegionNum":1,"RegionCategory":"综合性期刊","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"MULTIDISCIPLINARY SCIENCES","Score":null,"Total":0}
Selective light-driven methane oxidation to ethanol
Methane (CH4) photocatalytic upgrading to value-added chemicals, especially C2 products, is significant yet challenging due to sluggish energy/mass transfer and insufficient chemical driven-force in single photochemical process. Herein, we realize solar-driven CH4 oxidation to ethanol (C2H5OH) on crystalline carbon nitride (CCN) modified with Cu9S5 and Cu single atoms (Cu9S5/Cu-CCN). The integration of photothermal effect and photocatalysis overcomes CH4-to-C2H5OH conversion bottlenecks, with Cu9S5 as a hotspot to convert solar-energy to heat. In-situ characterizations demonstrate that Cu single atoms play as electron acceptor for O2 reduction to ·OOH/ · OH, while Cu9S5 acts as hole acceptor and site for CH4 adsorption, C − H activation, and C − C coupling. Theoretical calculations demonstrate that Cu9S5/Cu-CCN reduces C − C coupling energy barrier by stabilizing ·CH3 and ·CH2O. Impressively, C2H5OH productivity reaches 549.7 μmol g–1 h–1, with selectivity of 94.8% and apparent quantum efficiency of 0.9% (420 nm). This work provides a sustainable avenue for CH4 conversion to value-added chemcials.
期刊介绍：
Nature Communications, an open-access journal, publishes high-quality research spanning all areas of the natural sciences. Papers featured in the journal showcase significant advances relevant to specialists in each respective field. With a 2-year impact factor of 16.6 (2022) and a median time of 8 days from submission to the first editorial decision, Nature Communications is committed to rapid dissemination of research findings. As a multidisciplinary journal, it welcomes contributions from biological, health, physical, chemical, Earth, social, mathematical, applied, and engineering sciences, aiming to highlight important breakthroughs within each domain.
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