润湿性导向电沉积自支撑铁族金属膜多结构-析氢性能协调机制

The self-supported and non-noble metal catalysts with high activity and good stability at fluctuant and large current density for hydrogen evolution reaction (HER) are urgently needed for water electrolysis driven by renewable energy. Metal electrodeposition in aqueous solution is the best method to prepare self-supported catalysts. However, the adsorption and separation of hydrogen bubbles is indispensable due to hydrogen evolution side reaction during electrodeposition, which will affect the structure and properties of metal films. At present, However, at present, the most of studies were focused on the effect regularities of various conditions on metal electrodeposition. The wettability is the key factor to determine the adsorption and separation of bubbles. The evolution regularity of surface structure of electrodeposited metal films is not understood based on the adjustment of wettability. Therefore, the structure and properties of electrodeposited metal films can not be adjusted accurately. In this item, a novel method that self-supported iron-group metal films as HER electrode with various structures are electrodeposited based on the adjustment function of wettability is proposed. The relationships between wettability and surface structures of electrodeposited metal films are studied. The evolution regularities of metal reduction kinetics and bubble separation characteristics during metal electrodeposition are investigated. The formation mechanism of different mirco-nano structure is analyzed. The long-term effects of wettability on the evolution of micro-nano structure are analyzed. The adjustment mechanism of surface structure of electrodeposited metal films by wettability is discussed. The suitable structure and preparation method of self-supported iron-group metal films with the coordinated catalytic activity and stability at large current density are obtained. By this item, it provides theoretical direction for the preparation of HER electrode with good properties. The method also can be applied to fabricate compact-rough-porous metal films with various structure and properties.

催化活性高、波动性大电流稳定性好的自支撑非贵金属析氢电极是可再生能源驱动的水电解制氢过程节能的迫切需求。水溶液金属电沉积是制备自支撑薄膜状催化剂的最佳方法。然而，伴随的氢气泡析出-分离几乎不可避免，对薄膜构效调控起关键作用。现有金属电沉积侧重于宏观工艺的规律性研究，没有从决定气泡吸附分离的本质性质即润湿性出发，来认识电沉积金属表面结构的演化机制，致使薄膜构效定向调控难。本项目提出润湿性导向电沉积多结构自支撑铁族金属薄膜析氢电极新方法，重点研究润湿性对电沉积铁族金属膜多结构演变的作用规律，明确润湿性调节下气泡析出-金属还原动力学，解析差异性微纳结构形成与动态演变的长效性原理，阐释润湿性的导向机制，掌握催化活性和大电流稳定性匹配协调的自支撑铁族金属薄膜结构及其导向电沉积方法。本项目将为定向制备综合性能优异的析氢电极提供理论指导，也可扩展应用于可控电沉积平整-粗糙-多孔的多功能金属薄膜。

水溶液金属电沉积是制备自支撑薄膜状金属电极材料的最佳方法之一。然而，电沉积过程伴随的氢气泡析出-分离不可避免，将显著影响电沉积金属薄膜的结构和性能。润湿性是气泡吸附分离的本质驱动力。鉴于比，本项目创新性提出润湿性导向电沉积多结构自支撑铁族金属薄膜新方法。围绕项目核心思路和关键科学问题，获得了基于液相和固相的润湿性调节策略，解析了液相调节下电沉积金属薄膜微纳结构与表面润湿性动态演变行为，探明了固相调节润湿性对气泡分离和电沉积多孔金属薄膜结构的作用规律，阐释了润湿性导向电沉积多孔金属薄膜结构调节机理，提出了具有优异大电流全水电解性能的自支撑相分离Co-P基多孔金属薄膜，设计制备了自支撑多孔NixFe–S/NiFe2O4异质结析氢和析氧双功能电催化剂。在此基础上，扩展研究制备了气-液-固界面电化学构筑高负载、自支撑多孔Co-P基铝离子电池正极。本项目研究成果将为电沉积金属薄膜在平整-粗糙-多孔间的可控调节和制备综合性能优异的功能电极材料提供理论基础和技术支撑。基于上述研究，在Adv Mater等高水平期刊发表论文14篇，其中SCI论文13篇（IF>10 共5篇），申请发明专利3项（其中授权2项）；出站博士后1名，培养硕/博研究生6名（其中已毕业3名）；培养青年科技骨干4名，其中负责人入选“万人计划”青年拔尖人才，参与骨干晋升副高级专业技术职称1名，获高等学校科学研究优秀成果奖科学技术自然科学二等奖。