Herein, we propose a fast and scalable synthesis of a triazine based hierarchically conjugated covalent organic polymer under solvent and additive free conditions through a single step process. The synthesized material CCTP (Cyanuric Chloride-Thiourea-Polymer) was thoroughly characterized by various physicochemical techniques. The CCTP exhibited regular sponginess and excellent chemical as well as thermal stability. The solvent and additive free approach for CCTP synthesis provides a sustainable alternative for classical solvothermal methods. The CCTP was immobilized with Pd (0) and subsequently a heterogeneous material Pd@CCTP was obtained, which was used as an efficient catalyst for the hydrogenation of nitroarenes. The rate constant and E_a were measured to be 2.08 × 10⁻² s⁻¹ and 15.67 kJ mol⁻¹ respectively and thereafter other thermodynamic parameters like ΔH, ΔS and ΔG for the hydrogenation of p-nitrophenol were also calculated. The obtained results indicate that the catalytic hydrogenation of p-nitrophenol is a non-spontaneous and endothermic process. We have also investigated the effect of surfactants (NH₄OH, FA, and N₂) on the reaction performance, and consequently NH₄OH and FA both slow down the reaction while N₂ doesn't affect the reaction medium. Further, we calculated the rate constant for the hydrogenation of 2,4-dinitrophenol and 2,4,6-trinitrophenol. An array of nitroarenes were further reduced to extend the substrate scope at RT; high TOFs were observed. Besides, Pd@CCTP showed excellent reusability in hydrogenation reactions without evident performance falloff.

中文翻译：

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用于硝基芳烃加氢的Pd受限的共轭共价共价有机聚合物：催化，动力学，热力学和机理

在本文中，我们提出了通过一步法在无溶剂和无添加剂条件下快速，可扩展地合成基于三嗪的分层共轭共价有机聚合物的方法。通过各种物理化学技术对合成材料CCTP（氰尿酰氯-硫脲-聚合物）进行了全面表征。CCTP表现出规则的海绵状，优异的化学和热稳定性。CCTP合成的无溶剂和无添加剂方法为经典的溶剂热方法提供了一种可持续的替代方法。将CCTP固定在Pd（0）上，随后获得非均相材料Pd @ CCTP，将其用作硝基芳烃加氢的有效催化剂。测得的速率常数和E _a为2.08×10 ^-2分别为s ^-1和15.67 kJ mol ^-1，其后还计算了对硝基苯酚氢化的其他热力学参数，例如ΔH，ΔS和ΔG。所得结果表明对硝基苯酚的催化氢化是非自发的且吸热的过程。我们还研究了表面活性剂（NH ₄ OH，FA和N ₂）对反应性能的影响，因此NH ₄ OH和FA都会减慢反应，而N ₂不会影响反应介质。此外，我们计算了2,4-二硝基苯酚和2,4,6-三硝基苯酚氢化的速率常数。进一步还原了一系列硝基芳烃，以扩展室温下的底物范围；观察到较高的TOF。此外，Pd @ CCTP在加氢反应中显示出极好的可重复使用性，而性能没有明显下降。