Lu Chunshan, Zhang Xuejie, Qi Yani, Ji Haoke, Zhu Qianwen, Wang Hao, Zhou Yebin, Feng Zhenlong, Li Xiaonian
State Key Laboratory Breeding Base of Green Chemistry Synthesis Technology Zhejiang University of Technology Hangzhou 310014 China.
ChemistryOpen. 2019 Jan 24;8(1):87-96. doi: 10.1002/open.201800227. eCollection 2019 Jan.
A nitrogen-carbon framework with the thickness of several molecules was fabricated through a straightforward nitrogen-doping strategy, in which specially designed surface-oxygen-containing groups (SOGs) first introduced onto the porous carbon support were used to guide the generation of a surface-nitrogen-containing structure through condensation reactions between SOGs and the amidogen group of organic amines under hydrothermal conditions. The results indicate that different kinds of SOGs generate different types and abundances of N species. The CO-releasing groups are apt to form a high proportion of amino groups, whereas the CO-releasing groups, especially carboxyl and lactones, are mainly transformed into pyrrolic-type nitrogen. In the framework with dominant pyrrolic-type nitrogen, an electron-rich Pd activated site composed of Pd, pyrrolic-type N and C is built, in which electron transfer occurs from N to C and Pd atoms. This activated site contributes to the formation of electron-rich activated hydrogen and desorption of p-chloroaniline, which work together to achieve the superior selectivity about 99.90 % of p-chloroaniline and the excellent reusable performance. This strategy not only provides low-cost, nitrogen-doped carbon materials, but also develops a new method for the fabrication of different kinds of nitrogen species structures.
通过一种直接的氮掺杂策略制备了一种厚度为几个分子的氮-碳骨架，其中首先引入到多孔碳载体上的特殊设计的含表面氧基团（SOGs）用于在水热条件下通过SOGs与有机胺的氨基之间的缩合反应来引导含表面氮结构的生成。结果表明，不同种类的SOGs会产生不同类型和丰度的氮物种。CO释放基团易于形成高比例的氨基，而CO释放基团，尤其是羧基和内酯，主要转化为吡咯型氮。在以吡咯型氮为主的骨架中，构建了由Pd、吡咯型N和C组成的富电子Pd活化位点，其中电子从N转移到C和Pd原子。该活化位点有助于富电子活化氢的形成和对氯苯胺的脱附，共同作用实现了对氯苯胺约99.90%的优异选择性和出色的可重复使用性能。该策略不仅提供了低成本的氮掺杂碳材料，还开发了一种制备不同种类氮物种结构的新方法。
