IDEAS home Printed from https://ideas.repec.org/a/nat/natcom/v16y2025i1d10.1038_s41467-025-57567-2.html
   My bibliography  Save this article

Photoelectrocatalytic Cl-mediated C(sp3)–H aminomethylation of hydrocarbons by BiVO4 photoanodes

Author

Listed:
  • Anzai Shi

    (94 Weijin Road)

  • Pengfei Xie

    (94 Weijin Road)

  • Yanwei Wang

    (94 Weijin Road)

  • Youai Qiu

    (94 Weijin Road)

Abstract

Interfacial photoelectrochemistry at photoanodes has been extensively researched for solar energy conversion, but its application for the production of high-value-added chemical compounds in organic chemistry still presents challenges. Herein, we report photoelectrocatalytic Cl-mediated C(sp3)–H aminomethylation of alkanes with self-developed and reusable BiVO4 photoanodes. The swift condensation of aniline with aldehydes, along with the decrease of the electricity input of aniline by photogenerated holes in the BiVO4 photoanodes, work together to prevent excessive oxidation of aniline, leading to high yields of the desired product. Mechanistic experiments demonstrate that Cl- ions, as the key mediators, could be attracted to holes in the photoanodes and oxidized to form the Cl2. This is followed by light-promoted homolytic cleavage of Cl2, generating Cl radicals that efficiently abstract hydrogen atoms from hydrocarbons. This work opens an avenue for interfacial photoelectrochemical organic synthesis and demonstrates a potential method for optimizing solar energy conversion into fuels.

Suggested Citation

  • Anzai Shi & Pengfei Xie & Yanwei Wang & Youai Qiu, 2025. "Photoelectrocatalytic Cl-mediated C(sp3)–H aminomethylation of hydrocarbons by BiVO4 photoanodes," Nature Communications, Nature, vol. 16(1), pages 1-14, December.
    • Handle: RePEc:nat:natcom:v:16:y:2025:i:1:d:10.1038_s41467-025-57567-2
    DOI: 10.1038/s41467-025-57567-2
    as

    Download full text from publisher

    File URL: https://www.nature.com/articles/s41467-025-57567-2
    File Function: Abstract
    Download Restriction: no
    File URL: https://libkey.io/10.1038/s41467-025-57567-2?utm_source=ideas
    LibKey link: if access is restricted and if your library uses this service, LibKey will redirect you to where you can use your library subscription to access this item
    ---><---

    References listed on IDEAS

    as
    1. Long Zou & Siqi Xiang & Rui Sun & Qingquan Lu, 2023. "Selective C(sp3)–H arylation/alkylation of alkanes enabled by paired electrocatalysis," Nature Communications, Nature, vol. 14(1), pages 1-10, December.
    2. Zhenhua Li & Lan Luo & Min Li & Wangsong Chen & Yuguang Liu & Jiangrong Yang & Si-Min Xu & Hua Zhou & Lina Ma & Ming Xu & Xianggui Kong & Haohong Duan, 2021. "Photoelectrocatalytic C–H halogenation over an oxygen vacancy-rich TiO2 photoanode," Nature Communications, Nature, vol. 12(1), pages 1-13, December.
    3. Dongfeng Yang & Zhipeng Guan & Yanan Peng & Shuxiang Zhu & Pengjie Wang & Zhiliang Huang & Hesham Alhumade & Dong Gu & Hong Yi & Aiwen Lei, 2023. "Electrochemical oxidative difunctionalization of diazo compounds with two different nucleophiles," Nature Communications, Nature, vol. 14(1), pages 1-8, December.
    4. Jinghao Wang & Siyang Li & Caoyu Yang & Huiwen Gao & Lulu Zuo & Zhiyu Guo & Pengqi Yang & Yuheng Jiang & Jian Li & Li-Zhu Wu & Zhiyong Tang, 2024. "Photoelectrochemical Ni-catalyzed cross-coupling of aryl bromides with amine at ultra-low potential," Nature Communications, Nature, vol. 15(1), pages 1-8, December.
    5. Tengfei Li & Takahito Kasahara & Jingfu He & Kevan E. Dettelbach & Glenn M. Sammis & Curtis P. Berlinguette, 2017. "Photoelectrochemical oxidation of organic substrates in organic media," Nature Communications, Nature, vol. 8(1), pages 1-5, December.
    6. Pengfei Li & Chengcheng Guo & Siyi Wang & Dengke Ma & Tian Feng & Yanwei Wang & Youai Qiu, 2022. "Facile and general electrochemical deuteration of unactivated alkyl halides," Nature Communications, Nature, vol. 13(1), pages 1-8, December.
    7. Sanghyun Bae & Thomas Moehl & Erin Service & Minjung Kim & Pardis Adams & Zhenbin Wang & Yuri Choi & Jungki Ryu & S. David Tilley, 2024. "A hole-selective hybrid TiO2 layer for stable and low-cost photoanodes in solar water oxidation," Nature Communications, Nature, vol. 15(1), pages 1-9, December.
    Full references (including those not matched with items on IDEAS)

    Most related items

    These are the items that most often cite the same works as this one and are cited by the same works as this one.
    1. Jinghao Wang & Siyang Li & Caoyu Yang & Huiwen Gao & Lulu Zuo & Zhiyu Guo & Pengqi Yang & Yuheng Jiang & Jian Li & Li-Zhu Wu & Zhiyong Tang, 2024. "Photoelectrochemical Ni-catalyzed cross-coupling of aryl bromides with amine at ultra-low potential," Nature Communications, Nature, vol. 15(1), pages 1-8, December.
    2. Ziyu Mi & Yuke Li & Chao Wu & Mingsheng Zhang & Xun Cao & Shibo Xi & Jia Zhang & Wan Ru Leow, 2025. "CoOx clusters-decorated IrO2 electrocatalyst activates NO3- mediator for benzylic C-H activation," Nature Communications, Nature, vol. 16(1), pages 1-10, December.
    3. Xiangyu Meng & Chuntong Zhu & Xin Wang & Zehua Liu & Mengmeng Zhu & Kuibo Yin & Ran Long & Liuning Gu & Xinxing Shao & Litao Sun & Yueming Sun & Yunqian Dai & Yujie Xiong, 2023. "Hierarchical triphase diffusion photoelectrodes for photoelectrochemical gas/liquid flow conversion," Nature Communications, Nature, vol. 14(1), pages 1-13, December.
    4. Mengjie Jiao & Jie Zhang & Minyan Wang & Hongjian Lu & Zhuangzhi Shi, 2024. "Metallaphotoredox deuteroalkylation utilizing thianthrenium salts," Nature Communications, Nature, vol. 15(1), pages 1-11, December.
    5. Weicheng Shen & Tingting Hu & Xueyan Liu & Jiajia Zha & Fanqi Meng & Zhikang Wu & Zhuolin Cui & Yu Yang & Hai Li & Qinghua Zhang & Lin Gu & Ruizheng Liang & Chaoliang Tan, 2022. "Defect engineering of layered double hydroxide nanosheets as inorganic photosensitizers for NIR-III photodynamic cancer therapy," Nature Communications, Nature, vol. 13(1), pages 1-14, December.
    6. Zhenhua Li & Lan Luo & Min Li & Wangsong Chen & Yuguang Liu & Jiangrong Yang & Si-Min Xu & Hua Zhou & Lina Ma & Ming Xu & Xianggui Kong & Haohong Duan, 2021. "Photoelectrocatalytic C–H halogenation over an oxygen vacancy-rich TiO2 photoanode," Nature Communications, Nature, vol. 12(1), pages 1-13, December.
    7. Yanwei Wang & Qian Wang & Lei Wu & Kangping Jia & Minyan Wang & Youai Qiu, 2024. "Electroreduction of unactivated alkenes using water as hydrogen source," Nature Communications, Nature, vol. 15(1), pages 1-10, December.
    8. Bailin Tian & Fangyuan Wang & Pan Ran & Luhan Dai & Yang Lv & Yuxia Sun & Zhangyan Mu & Yamei Sun & Lingyu Tang & William A. Goddard & Mengning Ding, 2024. "Parameterization and quantification of two key operando physio-chemical descriptors for water-assisted electro-catalytic organic oxidation," Nature Communications, Nature, vol. 15(1), pages 1-14, December.
    9. Yang Liu & Huishan Shang & Bing Zhang & Dongpeng Yan & Xu Xiang, 2024. "Surface fluorination of BiVO4 for the photoelectrochemical oxidation of glycerol to formic acid," Nature Communications, Nature, vol. 15(1), pages 1-12, December.
    10. Kai Sun & Chang Ge & Xiaolan Chen & Bin Yu & Lingbo Qu & Bing Yu, 2024. "Energy-transfer-enabled photocatalytic transformations of aryl thianthrenium salts," Nature Communications, Nature, vol. 15(1), pages 1-9, December.
    11. Zhiwei Zhao & Ranran Zhang & Yaowen Liu & Zile Zhu & Qiuyan Wang & Youai Qiu, 2024. "Electrochemical C−H deuteration of pyridine derivatives with D2O," Nature Communications, Nature, vol. 15(1), pages 1-9, December.
    12. Min Liu & Tian Feng & Yanwei Wang & Guangsheng Kou & Qiuyan Wang & Qian Wang & Youai Qiu, 2023. "Metal-free electrochemical dihydroxylation of unactivated alkenes," Nature Communications, Nature, vol. 14(1), pages 1-9, December.
    13. Meng He & Rui Li & Chuanqi Cheng & Cuibo Liu & Bin Zhang, 2024. "Microenvironment regulation breaks the Faradaic efficiency-current density trade-off for electrocatalytic deuteration using D2O," Nature Communications, Nature, vol. 15(1), pages 1-10, December.
    14. Panpan Ma & Ting Guo & Hongjian Lu, 2024. "Hydro- and deutero-deamination of primary amines using O-diphenylphosphinylhydroxylamine," Nature Communications, Nature, vol. 15(1), pages 1-9, December.
    15. Bo Wu & Ruihu Lu & Chao Wu & Tenghui Yuan & Bin Liu & Xi Wang & Chenyi Fang & Ziyu Mi & Surani Dolmanan & Weng Weei Tjiu & Mingsheng Zhang & Bingqing Wang & Zainul Aabdin & Sui Zhang & Yi Hou & Bote Z, 2025. "Pt/IrOx enables selective electrochemical C-H chlorination at high current," Nature Communications, Nature, vol. 16(1), pages 1-15, December.

    More about this item

    Statistics

    Access and download statistics

    Corrections

    All material on this site has been provided by the respective publishers and authors. You can help correct errors and omissions. When requesting a correction, please mention this item's handle: RePEc:nat:natcom:v:16:y:2025:i:1:d:10.1038_s41467-025-57567-2. See general information about how to correct material in RePEc.

    If you have authored this item and are not yet registered with RePEc, we encourage you to do it here. This allows to link your profile to this item. It also allows you to accept potential citations to this item that we are uncertain about.

    If CitEc recognized a bibliographic reference but did not link an item in RePEc to it, you can help with this form .

    If you know of missing items citing this one, you can help us creating those links by adding the relevant references in the same way as above, for each refering item. If you are a registered author of this item, you may also want to check the "citations" tab in your RePEc Author Service profile, as there may be some citations waiting for confirmation.

    For technical questions regarding this item, or to correct its authors, title, abstract, bibliographic or download information, contact: Sonal Shukla or Springer Nature Abstracting and Indexing (email available below). General contact details of provider: http://www.nature.com .

    Please note that corrections may take a couple of weeks to filter through the various RePEc services.

    IDEAS is a RePEc service. RePEc uses bibliographic data supplied by the respective publishers.