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 ZnCoS_x/Fe₃S₄ heterojunction photocatalyst is designed with asymmetric adsorption sites and excellent PNRR performance. The heterojunction possesses a hollow-on-hollow superstructure: Fe₃S₄ nanocrystal-modified ZnCoS_x nanocages as building blocks assemble into spindle-shaped particles with a spindle-like cavity. Both Fe₃S₄ and ZnCoS_x 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，用于增强氮气光还原


光催化氮还原反应 （PNRR） 为可持续氨 （NH₃） 合成具有巨大的前景。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 ZnCoS_x/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 纳米晶改性的 ZnCoS_x 纳米笼作为构建块组装成具有纺锤形腔的纺锤形颗粒。Fe₃S₄ 和 ZnCoS_x 均具有近红外活性，可有效利用全光谱光。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 的不对称侧面吸附模式，有利于 N₂ 分子的极化和活化。结合中空上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。