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[Display omitted] Constructing donor–acceptor structures in polymeric carbon nitride (CN) provides an attractive pathway for facilitating charge carrier separation in photocatalytic reactions. However, achieving the implantation of donor or acceptor moieties at molecule level precision remains challenging. Here we develop a three-dimensional (3D) porous thiophene implanted carbon nitride (TCN) with donor–acceptor structure via a supramolecular assembly strategy. The specific-designed triazine derivatives with similar hydrogen bonding sites allow for the uniform introduction of thiophene groups at molecule level precision during the supramolecular assemble stage. The electron-donating thiophene groups in TCN can continuously tune electronic band structure, expand visible light absorption range, and promote charge carriers' separation. The optimized properties enable TCN-3 an outstanding H 2 evolution rate of 5620 μmol h−1 g−1, greatly exceeding bulk CN (95 μmol h−1 g−1). Briefly, our work may offer opportunities to prepare highly active photocatalysts with molecule level precise donor–acceptor structure. [ABSTRACT FROM AUTHOR]

[Display omitted] • A loofah-like carbon nitride sponge(LCN) is successfully synthesized. • The LCN features 3D hierarchical porous structure and ultrathin thickness. • Oxygen doping and nitrogen vacancies engineering are simultaneously constructed. • The LCN shows excellent photocatalytic activity and stability. • The mechanism of transfer hydrogenation with water as hydrogen source is revealed. The vigorous development of photocatalytic water splitting technology has laid the foundation for the photocatalytic transfer hydrogenation of organic substrates to produce the high value-added chemicals using water as hydrogen source. Nevertheless, the high dissociation energy of the O–H bond impedes its academic progress and the practical applications. Herein, we synthesize a 3D hierarchical porous loofah-like carbon nitride sponge (LCN) with ultrathin thickness via the supramolecular pre-organization coupling with the oxidation etching process, in which the heterogeneous oxygen atoms and the nitrogen vacancies are in-situ engineered. On top of the adorable photocatalytic H 2 evolution (4812 μmol h−1 g−1), LCN associated with Pt cocatalyst reveals a conversion rate of 96.5 % towards the hydrogenation of 4-nitrophenol, substantially superior to the reference experiment (8.3 %). Further based on the isotope-labeling tests and the density functional theory calculations, the photo-generated H0 from water is clarified to be the direct reducing agent, tactfully skipping the hydrogen extraction step in the traditional path. This work provides a green and sustainable methodology to transfer the solar energy to the valuable fine chemicals, as well as highlights the importance of the 3D hierarchical porous structure to the catalytic activity. [ABSTRACT FROM AUTHOR]