Scandurra Antonino, Iacono Valentina, Boscarino Stefano, Scalese Silvia, Grimaldi Maria Grazia, Ruffino Francesco
Department of Physics and Astronomy "Ettore Majorana", University of Catania, via Santa Sofia 64, 95123 Catania, Italy.
Institute for Microelectronics and Microsystems of National Research Council of Italy (CNR-IMM, Catania University Unit), via Santa Sofia 64, 95123 Catania, Italy.
Nanomaterials (Basel). 2023 Jan 30;13(3):561. doi: 10.3390/nano13030561.
Recently, hydrogen evolution reaction (HER) in alkaline media has received a renewed interest both in the fundamental research as well as in practical applications. Pulsed Laser Ablation in Liquid (PLAL) has been demonstrated as a very useful technique for the unconventional preparation of nanomaterials with amazing electro-catalyst properties toward HER, compared to those of nanomaterials prepared by conventional methods. In this paper, we compared the electro-sorption properties of hydrogen in alkaline media by Pt, Pd, PtPd, and Cu(OH) nanoparticles (NPs) prepared by PLAL. The NPs were placed onto graphene paper (GP). Noble metal particles have an almost spherical shape, whereas Cu(OH) presents a flower-bud-like shape, formed by very thin nanowalls. XPS analyses of Cu(OH) are compatible with a high co-ordination of Cu(II) centers by OH and HO. A thin layer of perfluorosulfone ionomer placed onto the surface of nanoparticles (NPs) enhances their distribution on the surface of graphene paper (GP), thereby improving their electro-catalytic properties. The proposed mechanisms for hydrogen evolution reaction (HER) on noble metals and Cu(OH) are in line with the adsorption energies of H, OH, and HO on the surfaces of Pt, Pd, and oxidized copper. A significant spillover mechanism was observed for the noble metals when supported by graphene paper. Cu(OH) prepared by PLAL shows a competitive efficiency toward HER that is attributed to its high hydrophilicity which, in turn, is due to the high co-ordination of Cu(II) centers in very thin Cu(OH) layers by OH and HO. We propose the formation of an intermediate complex with water which can reduce the barrier energy of water adsorption and dissociation.
最近，碱性介质中的析氢反应（HER）在基础研究和实际应用中都重新引起了人们的关注。与通过传统方法制备的纳米材料相比，液相脉冲激光烧蚀（PLAL）已被证明是一种非常有用的技术，可用于非常规制备具有惊人HER电催化性能的纳米材料。在本文中，我们比较了通过PLAL制备的Pt、Pd、PtPd和Cu(OH)纳米颗粒（NPs）在碱性介质中对氢的电吸附性能。这些NPs被放置在石墨烯纸（GP）上。贵金属颗粒几乎呈球形，而Cu(OH)呈现出由非常薄的纳米壁形成的花蕾状。Cu(OH)的XPS分析与Cu(II)中心与OH和HO的高配位情况相符。放置在纳米颗粒（NPs）表面的一层薄的全氟磺酸离聚物增强了它们在石墨烯纸（GP）表面的分布，从而改善了它们的电催化性能。提出的贵金属和Cu(OH)上析氢反应（HER）的机制与H、OH和HO在Pt、Pd和氧化铜表面的吸附能一致。当由石墨烯纸支撑时，观察到贵金属有显著的溢流机制。通过PLAL制备的Cu(OH)对HER显示出有竞争力的效率，这归因于其高亲水性，而高亲水性又是由于非常薄的Cu(OH)层中Cu(II)中心与OH和HO的高配位。我们提出与水形成中间络合物，这可以降低水吸附和解离的势垒能。
