Carbonaceous catalysts for photocatalysis and electrocatalysis with high specific surface by direct carbonization of hierarchical block copolymer architectures

碳质杂化材料作为载体和催化剂在电化学和电催化方面具有很大的潜力。所提出的项目的目的是将碳质杂化材料整合到三维分级结构中，以将碳质杂化材料和三维分级结构的固有优势（例如高表面积和容易接近催化活性位点）联合收割机结合。两个目标架构将实现和测试：光学透明的自有序纳米多孔阳极氧化铝（AAO）膜含有碳/二氧化钛（C-TiO 2）纳米管的可见光反射和阵列的独立的中孔碳/金属纳米粒子（C-NP）纳米棒的电催化通过复制AAO获得。这两种目标架构的特点是比光滑的薄膜配置显着更高的比表面积;与传统的介孔材料相比，对催化活性位点的访问将显着改善。为了制备目标结构，Steinhart和Kim开发了一种新的方法，即直接碳化纳米结构嵌段共聚物（BCP），AAO孔引入的层次结构包括C-TiO 2纳米管和介孔C-NP纳米棒的形貌轮廓。C-TiO 2纳米管的可见光在AAO膜具有约1000倍大的表面比光滑的薄膜配置每膜面积。这种结构使碳的催化无效光吸收最小化，因为只有薄的C-TiO 2层覆盖透明AAO膜的孔壁。AAO中的TiO 2纳米管可以潜在地用作流动反应器中的光催化组分。介孔C-NP纳米棒与电解质溶液的形貌接触界面是光滑介孔C-NP膜的11倍。与纳米级BCP畴结构相关的分级水平指导了覆盖AAO孔壁的C-TiO 2纳米管中TiO 2的空间分布。它还指导溶胀诱导的形态重建，在BCP纳米棒阵列中产生连续的中孔系统，其将被转化为中孔C-NP纳米棒阵列。将通过所选的模型反应与光滑对照样品进行比较，测试AAO中TiO 2纳米管的光催化性能和介孔C-NP纳米棒阵列的电催化性能。

Carbonaceous hybrid materials have considerable potential as support and catalyst in photocatalysis and electrocatalysis. Aim of the proposed project is integration of carbonaceous hybrid materials into three-dimensional hierarchical architectures to combine intrinsic advantages of carbonaceous hybrid materials and of three-dimensional hierarchical architectures, such as high surface area and facile access to catalytically active sites. Two target architectures will be realized and tested: optically transparent self-ordered nanoporous anodic alumina (AAO) membranes containing carbon/titania (C-TiO2) nanotubes for visible-light photocatalysis and arrays of freestanding mesoporous carbon/metal nanoparticle (C-NP) nanorods for electrocatalysis obtained by replicating AAO. Both target architectures will be characterized by significantly higher specific surface than smooth thin-film configurations; access to catalytically active sites will be significantly improved as compared to conventional mesoporous materials. To prepare the target architectures, a new approach developed by Steinhart and Kim, direct carbonization of nanostructured block copolymers (BCPs), will be applied.The hierarchical level introduced by the AAO pores comprises the topographic contour of the C-TiO2 nanotubes and the mesoporous C-NP nanorods. C-TiO2 nanotubes for visible-light photocatalysis in AAO membranes have ~1000 times larger surface per membrane area than smooth thin-film configurations. This architecture minimizes catalytically ineffective light absorption by carbon since only thin C-TiO2 layers cover the pore walls of the transparent AAO membranes. TiO2 nanotubes in AAO can potentially be used as photocatalytic component in flow reactors. The topographic contact interface of mesoporous C-NP nanorods to electrolyte solutions is 11 times larger than that of smooth mesoporous C-NP films. The hierarchical level related to the nanoscopic BCP domain structure directs the spatial distribution of TiO2 in C-TiO2 nanotubes covering the AAO pore walls. It also directs swelling-induced morphology reconstruction yielding continuous mesopore systems in BCP nanorod arrays that will be converted into mesoporous C-NP nanorod arrays. The photocatalytic performance of TiO2 nanotubes in AAO and the electrocatalytic performance of mesoporous C-NP nanorod arrays will be tested in comparison to smooth control samples by means of selected model reactions.