高效Co基硼氢化钠水解制氢催化剂的制备及其作用机制研究

Hydrogen generation from hydrolysis of sodium borohydride is very promising in commercial scale hydrogen production for the future hydrogen economy. To develop catalysts with low cost and high catalytic efficiency becomes the key to the whole hydrolysis process. In this proposal, we have designed a novel Co-based catalyst anchored on sulfonated graphene to carry on the research of sodium borohydride catalysis decomposition. In addition, controllable synthesis of nanocatalysts with well-defined composition, structure, size, and morphology at the special position on the surface of the graphene is also achieved. Sulfonated graphene not only improves its solubility in water but also offers binding sites for synergistic effect of Co-based catalyst, then achieve efficient electrocatalytic activity for hydrolysis of sodium borohydride. The chemical and physical characters of the catalysts, such as the micro-structures, chemical components, surface oxidation states and defects, would be characterized by EPMA, HRTEM XPS and so on. The sodium borohydride decomposition and catalytic mechanism would be further investigated based on the characterization, and would be referred to adjust the catalyst composition. We believe that this investigation will promote the hydrogen production efficiency, and supply a new approach for the catalyst of the highly catalytic activity and durability towards hydrolysis of sodium borohydride.

硼氢化钠水解制氢是一种高效清洁的规模制氢方法，低成本且高效催化剂的研发是整个水解过程的关键。本项目从催化剂载体入手，通过表面磺化石墨烯负载Co基金属催化剂实现催化剂组成、粒子大小、结构在载体表面的可控合成及硼氢化钠水解过程研究。磺化石墨烯在提高其水溶性的同时为具有协同效应的Co基催化剂提供原位组装的沉积位点，实现提高催化剂催化分散性和活性的目标。通过EPMA、HRTEM，XPS 等研究手段对其制备过程和产物结构进行表征，结合理论分析获得催化剂材料的组成结构及其它性质与硼氢化钠水解催化活性的深层次关系，进而指导新型高效催化材料的开发与合成，最终获得具有高效和高稳定性的新型催化剂体系. 项目研究力图在新型催化材料设计、催化分解机理方面取得突破，为提高硼氢化钠水解的整体制氢效率提供实验依据和理论指导。

NaBH4水解析氢是一种便捷、安全的氢气发生技术，备受研究者的关注。在NaBH4的水解过程中，催化剂扮演着十分重要的角色。因为在有合适催化剂存在的情况下，NaBH4的水解反应变得快速且更容易控制。研究人员也开发出各式各样的催化剂，用来有效提高NaBH4的析氢速率。许多贵金属，例如Ru、Pt、Pd、PtRu合金，常被用来作为NaBH4水解的催化剂。为了改善催化剂的分散性和水溶性，人们开发出了各种载体，如金属片、金属氧化物、无机非金属材料和碳材料等等。这些材料能够增加载体的比表面积，一定程度上防止催化剂团聚，从而明显地提升催化活性。目前，Co基、Ni基催化剂仍是众多催化剂中的主力军；本项目围绕着Co基、Ni基纳米催化剂的制备、表征和对NaBH4碱性溶液的催化性能展开了一系列的研究，具体表现为：（1）功能化石墨烯及碳纳米管负载Co基催化剂催化硼氢化钠水解析氢的研究；（2）Mo及W掺杂的Co基纳米催化剂的制备及对硼氢化钠水解析氢的催化性能研究；（3）MOFs及LDH为载体的纳米催化剂的制备及对硼氢化钠水解析氢的催化性能研究。探讨了引入物种对催化剂活性和耐久性的影响，阐明催化剂表面和结构与其活性及耐久性的构效关系，揭示了催化分解机理。.项目研究已发表SCI期刊收录论文1篇，其中影响因子3.0以上论文6篇，申请中国发明专利一项，培养硕士毕业生11名和1名在读博士研究生，获得广西自然科学二等奖一项。项目很好的完成了预期的研究目标和任务。