Reduction of nitroaromatics to the corresponding amines is a key process in the fine and bulk chemicals industry to produce polymers, pharmaceuticals, agrochemicals and dyes. However, their effective and selective reduction requires high temperatures and pressurized hydrogen and involves noble metal-based catalysts. Here we report on an earth-abundant, plasmonic nano-photocatalyst, with an excellent reaction rate towards the selective hydrogenation of nitroaromatics. With solar light as the only energy input, the chalcopyrite catalyst operates through the combined action of hot holes and photothermal effects. Ultrafast laser transient absorption and light-induced electron paramagnetic resonance spectroscopies have unveiled the energy matching of the hot holes in the valence band of the catalyst with the frontier orbitals of the hydrogen and electron donor, via a transient coordination intermediate. Consequently, the reusable and sustainable copper-iron-sulfide (CuFeS₂) catalyst delivers previously unattainable turnover frequencies, even in large-scale reactions, while the cost-normalized production rate stands an order of magnitude above the state of the art.

将硝基芳烃还原成相应的胺是精细和大宗化学品工业生产聚合物、药物、农用化学品和染料的关键工艺。然而，它们的有效和选择性还原需要高温和加压氢气，并涉及贵金属基催化剂。在这里，我们报告了一种地球上丰富的等离子体纳米光催化剂，它对硝基芳烃的选择性加氢具有出色的反应速率。以太阳光作为唯一的能量输入，黄铜矿催化剂通过热孔和光热效应的联合作用发挥作用。超快激光瞬态吸收和光诱导电子顺磁共振光谱揭示了催化剂价带中的热空穴通过瞬态配位中间体与氢和电子供体的前线轨道的能量匹配。因此，可重复使用和可持续的硫化铜铁（CuFeS₂ ) 催化剂提供了以前无法达到的周转频率，即使在大规模反应中也是如此，而成本归一化的生产率比现有技术高出一个数量级。