López-García Andrés, Domínguez-Saldaña Aitor, Carrillo Alfonso J, Navarrete Laura, Valls Maria I, García-Baños Beatriz, Plaza-Gonzalez Pedro J, Catala-Civera José Manuel, Serra José Manuel
Instituto de Tecnología Química, Universitat Politècnica de València-Consejo Superior de Investigaciones Científicas, Av. dels Tarongers, 46022 València, Spain.
Instituto ITACA, Universitat Politècnica de València, Camí de Vera, 46022 València, Spain.
ACS Nano. 2023 Dec 12;17(23):23955-23964. doi: 10.1021/acsnano.3c08534. Epub 2023 Nov 17.
Exsolution has emerged as a promising method for generating metallic nanoparticles, whose robustness and stability outperform those of more conventional deposition methods, such as impregnation. In general, exsolution involves the migration of transition metal cations, typically perovskites, under reducing conditions, leading to the nucleation of well-anchored metallic nanoparticles on the oxide surface with particular properties. There is growing interest in exploring alternative methods for exsolution that do not rely on high-temperature reduction via hydrogen. For example, utilizing electrochemical potentials or plasma technologies has shown promising results in terms of faster exsolution, leading to better dispersion of nanoparticles under milder conditions. To avoid limitations in scaling up exhibited by electrochemical cells and plasma-generation devices, we proposed a method based on pulsed microwave (MW) radiation to drive the exsolution of metallic nanoparticles. Here, we demonstrate the H-free MW-driven exsolution of Ni nanoparticles from lanthanum strontium titanates, characterizing the mechanism that provides control over nanoparticle size and dispersion and enhanced catalytic activity and stability for CO hydrogenation. The presented method will enable the production of metallic nanoparticles with a high potential for scalability, requiring short exposure times and low temperatures.
离析法已成为一种有前景的制备金属纳米颗粒的方法,其坚固性和稳定性优于浸渍等更传统的沉积方法。一般来说,离析法涉及过渡金属阳离子(通常是钙钛矿)在还原条件下的迁移,导致在氧化物表面形成具有特定性质的、牢固锚定的金属纳米颗粒。人们越来越有兴趣探索不依赖于通过氢气进行高温还原的离析替代方法。例如,利用电化学势或等离子体技术在更快离析方面已显示出有前景的结果,从而在更温和的条件下实现纳米颗粒更好的分散。为避免电化学电池和等离子体发生装置在放大过程中表现出的局限性,我们提出了一种基于脉冲微波(MW)辐射来驱动金属纳米颗粒离析的方法。在此,我们展示了从钛酸镧锶中无氢MW驱动离析镍纳米颗粒,表征了控制纳米颗粒尺寸和分散以及增强CO加氢催化活性和稳定性的机制。所提出的方法将能够生产具有高可扩展性潜力的金属纳米颗粒,所需暴露时间短且温度低。