高效一维纳米电催化剂的设计、制备及性能调控

One-dimensional (1D) motifs exhibit improved surface chemistry and catalytic properties. The controlled synthesis of alloyed 1D electrocatalysts in large scale with low cost is still challenging but very attractive. Especially, the 1D electrocaltysts with various fine structures, such as ultrathin size, porosity and rough surface, will lead to increased surface areas that provide more active sites and increase Pt utilization per mass. In this project, strong efforts in developing large-scale synthesis method will be explored to meet the requirements from the proactical application. We will focus on the study of the influences of the composition, size, morphology on the electrochemical activity and stability to establish the correlation of such physical and chemical parameters with electrochemical performance. Such correlation will play an important role in reasonable design and synthesis of electrocatalysts with higher activity and stability, realizing the unification of structure design and performance control. In search for further improving the activity and stability based on the most studied 1D electrocatalysts, how to assemble 1D electrolcatalysts to form macroscopic assemblies such as films or three dimensional network electrocatalysts will be explored also due to their advantages such as higher structural stability, effective electron and mass transport. At the same time, we will develop new approaches to prepare nanocomposite electrocatalysts with high structural stability and catalytic performance using the prepared non-Pt 1D nanomaterials as catalytic carriers. In summary, this project aims to design and synthesis of 1D elelctrocatalysts with low cost, high platinum (Pt) utilization, high structural and electrocatalytic stability to promote the commercialization for the fuel cells through tuning the morphology, size and composition.

本项目拟以新型的高效一维纳米电催化剂的设计和功能为导向，通过调控电催化剂的形貌、尺寸和组分，获得低成本、高铂利用率、高结构稳定性和催化稳定性的优质电催化剂，推动和促进燃料电池商业化。面向应用需求，探索一维纳米电催化剂规模化可控制备方法，设计合成具有不同精细结构的一维纳米电催化剂，重点研究一维电催化剂的组分和结构与催化性能的相互关系和催化机理，进一步指导具备高催化活性电催化剂的设计和制备，实现结构设计和性能调控的统一；探索宏量制备一维纳米结构单元宏观组装体（如二维薄膜和三维网络结构材料）的有效组装技术和手段，系统研究此类宏观尺度组装材料的电催化性能；同时探索制备以非铂一维纳米电催化剂作为活性载体负载型功能纳米材料（即新型一维复合电催化剂）的新途径，充分发挥零维结构高表面积活性和一维结构高稳定性的优异性能，为制备具有商业应用前景的高活性和稳定性的新型电催化剂提供新思路。

本项目按项目任务书中内容计划实施，系统开展了新型高效一维纳米电催化剂的可控宏量合成、有序组装体及催化性能的研究。发展了两类高质量电催化材料的普适性合成方法，建立了一维电催化材料的宏量制备方法，实现了一系列一维过渡金属硫族化合物、合金纳米线、轻质一维碳基纳米结构材料等二十余种高活性电催化材料的可控合成，创制了新型等级结构一维异质结构硫化物，系统研究了电催化材料的结构、组成与表界面物性，阐明了纳米材料的电子效应、应力效应、协同效应与电催化性能的相互构效关系。重要成果如下：.建立了合成一维金属-硒-碲多元合金纳米线的普适性方法，宏量制备了一维高质量铜纳米线模板材料，以超细纳米线为牺牲模板，运用化学转化法，实现了一系列一维低铂合金纳米结构催化材料的近表面结构调控、三维表面构建和界面构筑；发展了化学嫁接、杂原子掺杂、晶相调控和缺陷工程等策略，创制了一系列基于硒化钴纳米带的高效析氢和产氧电极复合材料；发展了过渡金属盐协助热解有机小分子策略，普适合成了系列碳纳米结构材料，实现了碳纳米材料的功能掺杂和三维网络结构组装；建立了合成一维三元多节点鞘硫化物异质纳米棒和同质异相异质结构材料的新方法，精准合成了新型高效二氧化碳还原制多碳醇的铜基核-壳结构催化材料；揭示了纳米材料的结构、组成、物性与电催化性能之间的构效关系，为未来设计合成高效电催化材料提供了新思路。多项研究工作被Phys.Org、EurekAlert、Chemeurope.com、Scientific American等国际知名学术媒体亮点报道。.项目执行期间，已在Science, Nat. Nanotech., Nat. Catal., Sci. Adv., Nat. Commun., Chem. Rev., Chem. Soc. Rev., Acc. Chem. Res., J. Am. Chem. Soc., Angew. Chem. Int. Ed., Adv. Mater.等国际重要学术期刊上发表论文159篇（IF>10占70.4%）。授权国家发明专利37项。获国家自然科学二等奖。项目负责人2019年当选中国科学院院士。项目执行期间，2人获批国家基金委优秀青年基金，1人入选教育部“长江学者奖励计划”青年学者，5人入选中组部青年千人，1人获得香港求是基金会青年科学家奖。.