Photocatalytic nitrogen reduction reaction (PNRR) holds immense promise for sustainable ammonia (NH3) synthesis. However, few photocatalysts can utilize NIR light that carries over 50% of the solar energy for NH3 production with high performance. Herein, a dual NIR‐responsive S‐scheme ZnCoSx/Fe3S4 heterojunction photocatalyst is designed with asymmetric adsorption sites and excellent PNRR performance. The heterojunction possesses a hollow‐on‐hollow superstructure: Fe3S4 nanocrystal‐modified ZnCoSx nanocages as building blocks assemble into spindle‐shaped particles with a spindle‐like cavity. Both Fe3S4 and ZnCoSx are NIR active, allowing efficient utilization of full‐spectrum light. Moreover, an S‐scheme heterojunction is constructed that promotes charge separation. In addition, the Fe/Co dual‐metal sites at the interface enable an asymmetric side‐on adsorption mode of N2, favoring the polarization and activation of N2 molecules. In combination with the promoted mass transfer and active site exposure of hollow superstructure, a superior PNRR performance is achieved, with a high NH3 evolution rate of 2523.4 µmol g−1 h−1, an apparent quantum yield of 9.4% at 400 nm and 8% at 1000 nm, and a solar‐to‐chemical conversion efficiency of 0.32%. The work paves the way for the rational design of advanced heterojunction catalysts for PNRR.

中文翻译：

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具有不对称吸附位点的双近红外响应 S 型异质结，用于增强氮光还原


光催化氮还原反应 （PNRR） 为可持续氨 （NH3） 合成带来了巨大的希望。然而，很少有光催化剂可以利用近红外光，它携带了超过 50% 的太阳能，以高性能生产 NH3。在此，设计了一种双 NIR 响应 S 型 ZnCoSx/Fe3S4 异质结光催化剂，具有不对称吸附位点和优异的 PNRR 性能。异质结具有空心对空心的超结构：Fe3S4 纳米晶体修饰的 ZnCoSx 纳米笼作为构建单元组装成具有纺锤形腔的纺锤形颗粒。Fe3S4 和 ZnCoSx 都具有 NIR 活性，可以有效利用全光谱光。此外，构建了一个促进电荷分离的 S 型异质结。此外，界面处的 Fe/Co 双金属位点实现了 N2 的不对称侧向吸附模式，有利于 N2 分子的极化和活化。结合中空超层结构的促进传质和活性位点暴露，实现了卓越的 PNRR 性能，NH3 析出率高达 2523.4 μmol g-1 h-1，在 400 nm 处表观量子产率为 9.4%，在 1000 nm 处为 8%，日光-化学转换效率为 0.32%。这项工作为合理设计用于 PNRR 的先进异质结催化剂铺平了道路。