{"title":"在肖特基结中整合钯(I)原子,利用可见光驱动环境含氮物质和 CO 2 生产尿素","authors":"Wei-Yao Hu, Qi-Yuan Li, Dong Xu, Peng Gao, Pan-Zhe Qiao, Dong Li, Si-Yuan Xia, Xiu Lin, Jie-Sheng Chen, Xin-Hao Li","doi":"10.31635/ccschem.024.202404490","DOIUrl":null,"url":null,"abstract":"<p>The mass production of urea, the most widely used agricultural fertilizer, usually relies on energy- and carbon-intensive processes. The light-driven synthesis path has great potential for more sustainable techniques to produce urea from abundant naturally occurring resources, but this method suffers from the use of pure CO<sub>2</sub> and high-energy-driven forces (high temperature or ultraviolet light). Herein, we present a mild photocatalytic pathway for urea production from diverse nitrogenous species (such as NO<sub>3</sub><sup>−</sup>, NH<sub>3</sub>, and N<sub>2</sub>) and diluted CO<sub>2</sub> using visible light. We designed a palladium (Pd)-doped Schottky heterojunction, composed of graphene and titanium dioxide, as an effective photocatalyst to achieve on-farm urea generation. With the injection of visible-light-generated hot electrons from graphene to TiO<sub>2</sub>, the as-integrated Pd(I) centers with a special oxidation state of +1.36 in the TiO<sub>2</sub> lattice can initiate the universal reaction path of cascade reduction of NO<sub>3</sub><sup>−</sup>/N<sub>2</sub> to NH<sub>3</sub> and resulting C–N coupling of CO<sub>2</sub> with as-formed or added NH<sub>3</sub> to transform diverse nitrogenous species and CO<sub>2</sub> into urea. The urea yield over the <i>at.</i>-Pd@TiO<sub>2</sub>/Gr photocatalyst is 1.62 mmol g<sup>−1</sup> h<sup>−1</sup> under visible-light irradiation with an apparent quantum yield of 1.05% at 400 nm and 0.39% even at 700 nm.</p>","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":null,"pages":null},"PeriodicalIF":9.4000,"publicationDate":"2024-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Integrating Pd(I) Atoms in Schottky Junctions for Visible-Light-Driven Urea Production from Ambient Nitrogenous Species and CO 2\",\"authors\":\"Wei-Yao Hu, Qi-Yuan Li, Dong Xu, Peng Gao, Pan-Zhe Qiao, Dong Li, Si-Yuan Xia, Xiu Lin, Jie-Sheng Chen, Xin-Hao Li\",\"doi\":\"10.31635/ccschem.024.202404490\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>The mass production of urea, the most widely used agricultural fertilizer, usually relies on energy- and carbon-intensive processes. The light-driven synthesis path has great potential for more sustainable techniques to produce urea from abundant naturally occurring resources, but this method suffers from the use of pure CO<sub>2</sub> and high-energy-driven forces (high temperature or ultraviolet light). Herein, we present a mild photocatalytic pathway for urea production from diverse nitrogenous species (such as NO<sub>3</sub><sup>−</sup>, NH<sub>3</sub>, and N<sub>2</sub>) and diluted CO<sub>2</sub> using visible light. We designed a palladium (Pd)-doped Schottky heterojunction, composed of graphene and titanium dioxide, as an effective photocatalyst to achieve on-farm urea generation. With the injection of visible-light-generated hot electrons from graphene to TiO<sub>2</sub>, the as-integrated Pd(I) centers with a special oxidation state of +1.36 in the TiO<sub>2</sub> lattice can initiate the universal reaction path of cascade reduction of NO<sub>3</sub><sup>−</sup>/N<sub>2</sub> to NH<sub>3</sub> and resulting C–N coupling of CO<sub>2</sub> with as-formed or added NH<sub>3</sub> to transform diverse nitrogenous species and CO<sub>2</sub> into urea. The urea yield over the <i>at.</i>-Pd@TiO<sub>2</sub>/Gr photocatalyst is 1.62 mmol g<sup>−1</sup> h<sup>−1</sup> under visible-light irradiation with an apparent quantum yield of 1.05% at 400 nm and 0.39% even at 700 nm.</p>\",\"PeriodicalId\":9810,\"journal\":{\"name\":\"CCS Chemistry\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":9.4000,\"publicationDate\":\"2024-08-13\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"CCS Chemistry\",\"FirstCategoryId\":\"1085\",\"ListUrlMain\":\"https://doi.org/10.31635/ccschem.024.202404490\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"CCS Chemistry","FirstCategoryId":"1085","ListUrlMain":"https://doi.org/10.31635/ccschem.024.202404490","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Integrating Pd(I) Atoms in Schottky Junctions for Visible-Light-Driven Urea Production from Ambient Nitrogenous Species and CO 2
The mass production of urea, the most widely used agricultural fertilizer, usually relies on energy- and carbon-intensive processes. The light-driven synthesis path has great potential for more sustainable techniques to produce urea from abundant naturally occurring resources, but this method suffers from the use of pure CO2 and high-energy-driven forces (high temperature or ultraviolet light). Herein, we present a mild photocatalytic pathway for urea production from diverse nitrogenous species (such as NO3−, NH3, and N2) and diluted CO2 using visible light. We designed a palladium (Pd)-doped Schottky heterojunction, composed of graphene and titanium dioxide, as an effective photocatalyst to achieve on-farm urea generation. With the injection of visible-light-generated hot electrons from graphene to TiO2, the as-integrated Pd(I) centers with a special oxidation state of +1.36 in the TiO2 lattice can initiate the universal reaction path of cascade reduction of NO3−/N2 to NH3 and resulting C–N coupling of CO2 with as-formed or added NH3 to transform diverse nitrogenous species and CO2 into urea. The urea yield over the at.-Pd@TiO2/Gr photocatalyst is 1.62 mmol g−1 h−1 under visible-light irradiation with an apparent quantum yield of 1.05% at 400 nm and 0.39% even at 700 nm.
期刊介绍:
CCS Chemistry, the flagship publication of the Chinese Chemical Society, stands as a leading international chemistry journal based in China. With a commitment to global outreach in both contributions and readership, the journal operates on a fully Open Access model, eliminating subscription fees for contributing authors. Issued monthly, all articles are published online promptly upon reaching final publishable form. Additionally, authors have the option to expedite the posting process through Immediate Online Accepted Article posting, making a PDF of their accepted article available online upon journal acceptance.