激光液相烧蚀法制备IB金属团簇及其电催化性能研究

Noble metal catalysts play crucial roles in the process of clean energy utilization, however, the high price limits their wide application. Therefore, engineering cheap metallic catalysts becomes an urgent task for the scientists working in the new-energy material field. In this proposal, we suggest, on the basis of electrocatalytic reaction principles, that the adsorption energy of IB metals (Cu, Ag, Cu) can be modified by reducing their size to cluster scale (2-500 atoms), thus improving their catalytic properties for hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR). However, the metallic clusters obtained by routine wet-chemistry process are always coated by organic ligands which counteract the strengths of metallic clusters. So far, an effective mythology is still absent for the synthesis of ligand-free IB metallic clusters, and no successful work has been reported for the application of IB metallic clusters on the HER and ORR. The applicant worked on the synthesis of nanoparticles by using pulsed laser ablation in liquid (PLAL) for a long time, based on our primary results, we propose to prepare size-controllable, ligand-free IB metallic clusters by carefully tuning the PLAL parameters, investigate their electrocatalytic behavior for HER and ORR, and achieve low-cost, high-efficiency IB metal electrocatalysts. The smooth implementation of this project will pave a new way for controllable synthesis of clean metallic clusters, detect their physical and chemical properties, and demonstrate the potential and merits of metallic cluster for electrocatalytic applications.

贵金属催化剂在清洁能源领域扮演着重要的角色，但昂贵的价格限制了其大规模应用，设计廉价高效的催化剂一直是人们努力的方向。基于对催化机制的深入分析，本项目提出，将相对廉价的IB金属（Cu、Ag、Au）加工成团簇（含有2至500个原子），可以提升其对分子的吸附能，有望替代贵金属Pt，充当析氢反应（HER）和氧还原反应（ORR）的催化剂。但常规湿化学法合成的金属团簇被配体包裹，无法发挥催化优势，目前还缺少合成洁净金属团簇的有效工艺，IB金属团簇用于电催化HER和ORR尚属空白。申请人长期从事激光液相烧蚀法合成纳米材料，在前期工作基础上，申请人计划采用激光液相烧蚀工艺，获得表面洁净、尺寸可控的IB金属团簇，深入研究其电催化行为和机制，获得廉价高效的电还原催化剂。通过本项目的实施，将开辟可控合成金属团簇的新工艺，获得洁净金属团簇的物理化学性能，阐明IB金属团簇在电催化应用方面的潜力和优势。

贵金属催化剂在清洁能源领域扮演着重要的角色，但昂贵的价格限制了其大规模应用，设计廉价高效的催化剂一直是人们努力的方向。基于对催化机制的深入分析，本项目提出，将相对廉价的IB金属(Cu、Ag、Au)加工成团簇(含有2至500个原子)，可以提升其对分子的吸附能，有望替代贵金属Pt，充当析氢反应和氧还原反应的催化剂。研究结果表明，利用激光液相烧蚀法可以合成出超细尺寸IB金属团簇,通过调节激光能量改变金属颗粒的粒径，并且能在纳米颗粒中引入高密度堆垛层错，使IB金属对HER反应中间体的吸附作用极大的增强，从而将IB金属从低活性材料改性为超越Pt的超高活性催化剂。利用激光将IB金属与Ru金属进行固溶处理，得到IB金属单原子催化剂，为制造高性能催化剂提供了新思路。此外在本项目的支持下对激光合成高性能催化剂进行了深入的研究，合成了Pd、Ir、Ru、Zn金属纳米颗粒，Co3O4、FeCo2O4、RhOx氧化物纳米颗粒、多孔氢氧化钴镍纳米片、Ag@Co3O4和NiO/NiFe-LDH复合纳米粒子，这些催化剂在光解水、电解水和空气电池应用中展现了优异催化性能，说明激光法在合成催化剂方面具有突出的优势。同时开发了传统加工技术如热喷涂、搅拌摩擦等工艺制备自支撑的IB金属（铜、银）催化电极，更加适合工业应用。本项目共发表SCI论文40篇，包括2篇Nature Catalysis、1篇J. Am. Chem. Soc.、 2篇Angew. Chem. Int. Ed.、 2篇Adv. Mater. 、1篇 Acta Materialia、4篇ACS Catalysis、2篇Adv. Ener. Mater. 、1篇ACS Ener. Lett. 、2篇Adv. Funct. Mater. 、4篇Small、3篇J. Mater. Chem. A, 4篇 Chem. Comm. 申请专利4项，培养博士生7人，硕士生4人。超额圆满完成了研究目标。