近日，福州大学王心晨团队通过激活钙钛矿铁氧体中的晶格氧，实现了甲烷高效稳定的光热干重整。这一研究成果于2025年4月16日发表在《美国化学会杂志》上。

晶格氧（LO）介导的甲烷光热干重整（DRM）为合成气生产提供了一种有前景的方法。然而，由于催化剂中活化LO的困难，实现高DRM效率和耐用性仍然具有挑战性。在此，研究组证明，用Mn部分取代钙钛矿铁氧体（LaFeO₃）中的Fe位点会触发LO，使催化剂在用Ru改性后对光热DRM具有优异的活性和稳定性。Mn交换诱导了从La到Mn的电荷转移，这与入射的光激发电子相结合，重建了钙钛矿的电子结构，削弱了La-O-Mn键，促进了LO迁移。

同时，光生空穴迁移到表面LO，进一步增强了它们介导DRM的反应性。在光照下，催化剂表现出优异的合成气生产率（H₂:42.89 mol g_Ru^-1 h^-1，CO:54.92 mol g_Ru^-1 h^-1），同时稳定运行超过150小时。它还实现了0.9 s^-1的甲烷周转频率和15.3%的光化学能效率，为光驱动DRM性能树立了标杆。这项工作强调了金属氧化物中精确位点掺杂对微调LO活性的重要性，为通过光支持的Mars-van Krevelen机制进行的太阳能氧化还原反应的高效催化剂的制备提供了有价值的指导。

附：英文原文

Title: Activating Lattice Oxygen in Perovskite Ferrite for Efficient and Stable Photothermal Dry Reforming of Methane

Author: Jilong Li, Jiwu Zhao, Sibo Wang, Kang-Shun Peng, Bo Su, Kunlong Liu, Sung-Fu Hung, Meirong Huang, Guigang Zhang, Huabin Zhang, Xinchen Wang

Issue&Volume: April 16, 2025

Abstract: Lattice oxygen (LO)-mediated photothermal dry reforming of methane (DRM) presents a promising approach to syngas production. However, realizing high DRM efficiency and durability remains challenging due to the difficulty in activating LOs in catalysts. Herein, we demonstrate that partially substituting Fe sites in perovskite ferrite (LaFeO3) by Mn triggers LOs, bestowing the catalyst with superior activity and stability for photothermal DRM after modification with Ru. The Mn exchange induces a charge transfer from La to Mn, which combined with the incoming photoexcited electrons reconstructs the perovskite’s electronic structure, weakening the La–O–Mn bonds and facilitating the LO migration. Meanwhile, photogenerated holes migrate to surface LOs, further enhancing their reactivity to mediate DRM. Under light irradiation, the catalyst exhibits an outstanding syngas production rate (H2: 42.89 mol gRu–1 h–1, CO: 54.92 mol gRu–1 h–1) while stably operating over 150 h. It also achieves a methane turnover frequency of 0.9 s–1 and a light-to-chemical energy efficiency of 15.3%, setting a benchmark for light-driven DRM performance. This work underscores the significance of exact site doping in metal oxides to fine-tune LO activity, providing valuable guidance for fabricating efficient catalysts for solar-powered redox reactions proceeded via the light-supported Mars–van Krevelen mechanism.

DOI: 10.1021/jacs.5c03098

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.5c03098