Advanced Materials and Catalysis Group, Institute of Catalysis, Department of Chemistry, Zhejiang University, Hangzhou, 310028, P. R. China.
Department of Chemistry, Shanghai Key Lab of Molecular Catalysis and Innovative Materials, Collaborative Innovation Center of Chemistry for Energy Materials, Fudan University, Shanghai, 200438, P. R. China.
Small. 2022 Jan;18(2):e2104477. doi: 10.1002/smll.202104477. Epub 2021 Nov 5.
Synthesis of anisotropic carbonaceous nano- and micro-materials with well-ordered mesoporous structures has attracted increasing attention for a broad scope of applications. Although hard-templating method has been widely employed, overcoming the viscous forces to prepare anisotropic mesoporous materials is particularly challenging via the universal soft-templating method, especially from sustainable biomass as a carbon resource. Herein, the synthesis of biomass-derived nanowire-arrays based mesoporous nanorods and teeth-like superstructures is reported, through a simple and straightforward polyelectrolyte assisted soft-templating hydrothermal carbonization (HTC) approach. A surface energy induced interfacial assembly mechanism with the synergetic interactions between micelles, nanowire, nanorods, and polyelectrolyte is proposed. The polyelectrolyte acts not only as a stabilizer to decrease the surface energy of cylindrical micelles, nanowires and nanorods, but also as a structure-directing agent to regulate the oriented attachment and anisotropic assembly of micelles, nanowires, and nanorods. After a calcination treatment, the carbon nanorod and teeth-like superstructure are successfully coupled with Ru to directly produce supported catalysts for the hydrogen evolution reaction, exhibiting much better performance than the isotropic nanospheres based catalyst. This HTC approach will open up new avenues for the synthesis of anisotropic materials with various morphologies and dimensions, expanding the palette of materials selection for many applications.
具有有序介孔结构的各向异性碳纳米和微材料的合成因其广泛的应用而受到越来越多的关注。虽然硬模板法已经被广泛应用，但通过通用的软模板法克服粘性力来制备各向异性介孔材料尤其具有挑战性，特别是从可持续的生物质作为碳资源。在此，通过一种简单直接的聚电解质辅助软模板水热碳化（HTC）方法，报道了基于生物质衍生纳米线阵列的介孔纳米棒和齿状超结构的合成。提出了一种基于表面能的界面组装机制，其中胶束、纳米线、纳米棒和聚电解质之间存在协同相互作用。聚电解质不仅作为稳定剂降低了圆柱形胶束、纳米线和纳米棒的表面能，而且作为结构导向剂调节胶束、纳米线和纳米棒的定向附着和各向异性组装。经过煅烧处理后，碳纳米棒和齿状超结构成功地与 Ru 结合，直接生成用于析氢反应的负载型催化剂，其性能明显优于基于各向同性纳米球的催化剂。这种 HTC 方法将为具有各种形貌和尺寸的各向异性材料的合成开辟新途径，为许多应用的材料选择扩展了范围。
