偶联剂辅助的“NPs@Oxides”类核-壳结构跨尺度自组装及其甲烷干气重整性能研究

‘核-壳’纳米结构催化剂工程化是当前纳米催化领域极富挑战性的课题。提出了‘偶联剂’辅助的整装Foam/Fiber基体‘核-壳’纳米结构催化功能化新策略，即利用偶联剂的双向（配位络合和缩合偶联）化学键合作用，将不同的结构单元（如Ni纳米颗粒、SiO2壳层和Foam/Fiber基体）一步自组装而成整装‘核-壳’纳米结构催化剂，实现“核-壳结构催化特性-反应过程强化”的协同耦合。研究偶联剂结构与组成、过渡金属盐前体、Foam/Fiber骨架化学改性对‘核-壳’纳米结构一步跨尺度自组装的影响，阐明‘配位络合-界面化学反应偶联-核壳结构可控组装’多步协同匹配规律。侧重开展抗积炭、抗烧结、高导热甲烷干气重整Ni@Oxides/Foam(Fiber)整装催化剂的偶联剂辅助构筑，阐明Ni纳米颗粒尺寸和形态、Oxides壳孔结构和化学组成等物化特性以及基体结构与材质特性对抗烧结、抗积碳和热质传递的影响关系。

The ‘core-shell’ nanostructure is a promising protocol to inhibit the sintering of nanoparticles and enhance the catalyst stability, but its effective and efficient catalyst engineering remains significantly challenging. Herein, with the aid of well-defined cross-linking molecules, we propose a chemically and economically affordable strategy to catalytically functionalize the monolithic ‘Foam/Fiber’ substrates by the ‘core-shell’ nanostructure. Concretely, the different building blocks (such as Ni nanoparticles, SiO2 shell and Foam/Fiber substrate) can be precisely organized into the monolithic structured ‘core-shell’ catalyst in one step with the aid of APTES (one kind of cross-linking molecules) via properly controlling reactions (i.e., the chelation between Ni2+ and -NH2 in APTES, and the silanisation between -Si-O-CH2-CH3 and Foam/Fiber). Such monolithic structured ‘core-shell’ catalyst is able to collaboratively couple “the catalytic performance of ‘core-shell’ nanostructure and the reaction process intensification”. Effects of the kinds of cross-linking molecules, transition metal precursors, and Foam/Fiber chemical modifications, etc., will be systematically investigated on the one-step organization of this catalyst from nano- to macro-scales. And the one-step organization principle of ‘chelation, interface reaction coupling, and organization of ‘core-shell’ nanostructure via controllable hydrolysis reaction’ will be illustrated. In particular, the organization of the monolithic Foam/Fiber structured ‘Ni@Oxides’ catalysts with the aid of cross-linking molecules and their application in the dry reforming of methane are to be explored. The effects of Ni particles size and shape, the porous structure and composition of oxides-shell, and substrate structure and properties will be systematically studied on the sintering/coking resistance and heat/mass transfer property.