Abstract Metalporphyrin-based porous polymers supporting high dispersed Pd nanoparticle (NP) catalysts (HUST-1-Pd) were prepared with a novel solvent-knitting hyper-crosslinked polymer method using 5-, 10-, 15-, and 20-tetraphenylporphyrin (TPP) as building blocks. The N 2 sorption isotherms of the catalysts show that the HUST-1-Pd possesses many ultra-micropores and continuous mesopores. The NPs are assembled on tetraphenylporphyrin structures and show Pd-N 4 composition-dependent catalysis for methanolysis of ammonia borane (AB) and hydrogenation of aromatic nitro compounds to primary amines in methanol solutions at room temperature. The nano-palladium reduced by NaBH 4 has efficient catalytic activity for AB methanolysis. A variety of R-NO 2 derivatives were reduced selectively into R-NH 2 via palladium catalyzed tandem reactions with 5–30 min of reaction time with conversion yields reaching up to 90%. The derivatives also give excellent recycling performance (more than 10 times). Furthermore, the turnover frequency (TOF) can reach 87,209 h −1 . The HUST-1-Pd compounds represent a unique metal catalyst for hydrogenation reactions in a green environment without using pure hydrogen. Graphic Abstract A monodisperse Pd NPs embed in porphyrin-based microporous organic polymer was reported to catalyse the tandem dehydrogenation of ammonia borane and hydrogenation of R-NO 2 to R-NH 2 at room temperature. The catalyst is efficient and reusable in an environment-friendly process with short reaction times and high yields.

中文翻译：

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Pd纳米颗粒组装在金属卟啉基微孔有机聚合物上作为氨硼烷串联脱氢和硝基化合物加氢的高效催化剂

摘要 使用 5-、10-、15- 和 20-四苯基卟啉，采用新型溶剂编织超交联聚合物方法制备了负载高分散 Pd 纳米颗粒 (NP) 催化剂的金属卟啉基多孔聚合物 (HUST-1-Pd)。 TPP）作为构建块。催化剂的N 2 吸附等温线表明HUST-1-Pd 具有许多超微孔和连​​续中孔。NPs 组装在四苯基卟啉结构上，并显示出 Pd-N 4 组成依赖的催化作用，用于氨硼烷 (AB) 的甲醇分解和芳香硝基化合物在室温下在甲醇溶液中氢化为伯胺。NaBH 4 还原的纳米钯对AB甲醇分解具有有效的催化活性。多种R-NO 2 衍生物通过钯催化串联反应选择性还原为R-NH 2 ，反应时间为5-30 分钟，转化率高达90%。该衍生物还具有出色的回收性能（超过 10 倍）。此外，周转频率（TOF）可以达到87,209 h -1 。HUST-1-Pd 化合物代表了一种独特的金属催化剂，可在不使用纯氢的绿色环境中进行加氢反应。图形摘要 据报道，嵌入卟啉基微孔有机聚合物的单分散 Pd NPs 可在室温下催化氨硼烷的串联脱氢和 R-NO 2 氢化为 R-NH 2 。该催化剂高效且可重复使用，反应时间短，收率高，环境友好。