中国科学院固体物理研究所Yunyu Cai团队近日实现了利用d波段热载流子生成近红外光催化的宽带吸收Pt胶体。相关论文于2025年7月3日发表在《德国应用化学》杂志上。

作为纳米催化剂的过渡金属的带间和带内电子激发对热载流子的产生至关重要。与众所周知的Au， Ag和Cu纳米粒子（NPs）不同，它们通过吸收可见光直接形成热载流子，Pt NPs仍然具有有限的热载流子光生成能力。尽管如此，Pt独特的d波段结构允许在费米能量附近有高密度的电子态。它应该表现出光增强催化作用。

在有限差分时域（FDTD）计算的指导下，该团队利用Pt的电子结构，设计了一个由超小（≤5 nm） Pt NPs组成的亚100 nm胶体体（Cs），具有从可见光到近红外（NIR）波段的宽带吸收。Cs中的超小Pt NPs即使在低能电磁辐射激发下也能有效地产生热电子。

实现Cs的关键是利用激光生成的晶界富集的Mn₃O₄ NPs作为支架，高效、均匀地负载超小Pt NPs。这些Pt Cs在近红外波段辐照下表现出优异的过氧化氢酶（CAT）和氧化酶（OXD）模拟物的性能，使其成为光催化氧化反应的主题。此外，在体内利用Pt Cs进行肿瘤光动力治疗，可以获得前所未有的疗效和肿瘤生长抑制。

附：英文原文

Title: Pt Colloidosomes with Broadband Absorption for Near-Infrared Light Photocatalysis through d-Band Hot-Carriers Generation

Author: Sihan Ji, Xianglong Zhao, Pengfei Li, Peng Zheng, Haibin Tang, Vincenzo Amendola, Dongshi Zhang, Yunyu Cai, Kun Ma, Changhao Wang, Xiaohu Cheng, Shuxian Wei, Lingli Wu, Yixing Ye, Junfeng Wang, Changhao Liang

Issue&Volume: 2025-07-03

Abstract: Interband and intraband electronic excitations in transition metals as nanocatalysts are crucial for the generation of hot carriers. Unlike the well-known Au, Ag and Cu nanoparticles (NPs), in which hot carriers are directly formed by absorption of visible light, Pt NPs still have limited hot carriers photogeneration ability. Nonetheless, Pt's unique d-band structure permits a high density of electronic states near Fermi energy. It should have exhibited photoenhanced catalysis. Here, guided by Finite-Different-Time-Domain (FDTD) calculations, we take advantage of Pt electronic structure by designing a sub-100 nm colloidosome (Cs) consisted of ultrasmall (≤ 5 nm) Pt NPs with broadband absorption from visible to near-infrared (NIR) band. The ultrasmall Pt NPs in the Cs efficiently generated hot electrons even under excitation with the low-energy electromagnetic radiation. The key for realization of Cs is the exploitation of laser-generated, grain boundaries (GBs) enriched Mn3O4 NPs as scaffolds for the efficient and homogeneous loading of ultrasmall Pt NPs. These Pt Cs show outstanding performances as catalase (CAT) and oxidase (OXD) mimics under NIR band irradiation, allowing their use for photocatalysis of oxidation reactions. Besides, the in vivo exploitation of Pt Cs for tumor photodynamic therapy allowed unprecedented efficacy and caused tumor growth suppression.

DOI: 10.1002/anie.202509431

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202509431