| Summary: | The binary type-II heterojunction photocatalyst containing g-C<sub>3</sub>N<sub>4</sub> and polyoxoniobate (PONb, K<sub>7</sub>HNb<sub>6</sub>O<sub>19</sub>) with excellent H<sub>2</sub> production activity was synthesized by decorating via a facile hydrothermal method for the first time. The as-fabricated Nb–CN-0.4 composite displayed a maximum hydrogen evolution rate of 359.89 µmol g<sup>−1</sup> h<sup>−1</sup> without a co-catalyst under the irradiation of a 300 W Xenon Lamp, which is the highest among those of the binary PONb-based photocatalytic materials reported. The photophysical and photochemistry analyses indicated that the hydrogen evolution performance could be attributed to the formation of a type-II heterojunction, which could not only accelerate the transfer of photoinduced interfacial charges, but also effectively inhibit the recombination of electrons and holes. This work could provide a useful reference to develop an inexpensive and efficient photocatalytic system based on PONb towards H<sub>2</sub> production.
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