北京科技大学路军岭团队开发出了原子厚氧化物涂层刺激低温活性金属-载体相互作用增强催化。相关研究成果发表在2023年3月15日出版的《美国化学会杂志》。

活性金属-载体相互作用（RMSI）诱导双金属合金的形成，并为调节高级催化金属位点的电子和几何特性提供了一种有效的方法。然而，RMSI通常需要高温还原（>500°C），这大大限制了双金属成分变化的调节。

该文中，研究人员报道了原子厚的Pd纳米颗粒Ga₂O₃涂层能够在～250°C的更低温度下引发RMSI。最新的显微镜和原位光谱研究表明，低温RMSI引发了罕见的富Ga PdGa合金相的形成，这与高温还原后在传统Pd/Ga₂O₃催化剂中形成的Pd₂Ga相不同。在CO₂加氢反应中，富含Ga的合金相显著促进了甲醇和二甲醚的形成，比Pd/Ga₂O₃高出约5倍。原位红外光谱显示，富Ga相极大地有利于甲酸盐的形成及其随后的氢化，从提高生产率。

附：英文原文

Title: Atomically Thick Oxide Overcoating Stimulates Low-Temperature Reactive Metal–Support Interactions for Enhanced Catalysis

Author: Xinyu Liu, Qingqing Gu, Yafeng Zhang, Xiaoyan Xu, Hengwei Wang, Zhihu Sun, Lina Cao, Qimeng Sun, Lulu Xu, Leilei Wang, Shang Li, Shiqiang Wei, Bing Yang, Junling Lu

Issue&Volume: March 15, 2023

Abstract: Reactive metal–support interactions (RMSIs) induce the formation of bimetallic alloys and offer an effective way to tune the electronic and geometric properties of metal sites for advanced catalysis. However, RMSIs often require high-temperature reductions (>500 °C), which significantly limits the tuning of bimetallic compositional varieties. Here, we report that an atomically thick Ga2O3 coating of Pd nanoparticles enables the initiation of RMSIs at a much lower temperature of ～250 °C. State-of-the-art microscopic and in situ spectroscopic studies disclose that low-temperature RMSIs initiate the formation of rarely reported Ga-rich PdGa alloy phases, distinct from the Pd2Ga phase formed in traditional Pd/Ga2O3 catalysts after high-temperature reduction. In the CO2 hydrogenation reaction, the Ga-rich alloy phases impressively boost the formation of methanol and dimethyl ether ～5 times higher than that of Pd/Ga2O3. In situ infrared spectroscopy reveals that the Ga-rich phases greatly favor formate formation as well as its subsequent hydrogenation, thus leading to high productivity.

DOI: 10.1021/jacs.2c12046

Source: https://pubs.acs.org/doi/10.1021/jacs.2c12046