Formic acid (FA) is one of the most favorable chemical hydrogen storage materials for renewable energy transformation, the development of efficient heterogeneous catalysts for ultraclean H₂ generation from FA in the absence of any alkalis or additives under mild conditions remains a major challenge. Here, we present a porous organic polymer containing triphenylamine (TPA) and 2,6‐bis(1,2,3‐triazol‐4‐yl)pyridyl (BTP) units (TB‐POP). The ultrafine palladium nanoparticles (NPs) with an average size of 1.5±0.6 nm can be facilely generated using convenient methods and are uniformly dispersed over the TB‐POP support. TPA and BTP units are homogeneously arranged in the host framework of TB‐POP; they serve as effective alternatives of basic sites to deprotonate FA into formate intermediates. Pd@TB‐POP has demonstrated remarkable catalytic activity and high selectivity in additive‐free dehydrogenation of aqueous FA solution. The value of initial turnover frequency (TOF) at 50 °C is as high as 1344 h⁻¹. In sharp contrast, the use of sodium formate as an additive in the catalytic system results in the decrement of catalytic activity. The ultrafine palladium NPs are effectively immobilized during dehydrogenation of FA, and no aggregation of palladium NPs is observed after consecutive catalytic runs.

中文翻译：

---

功能化多孔有机聚合物促成高度分散的超细钯纳米粒子，实现甲酸的无添加剂脱氢

甲酸（FA）是可再生能源转化最有效的化学储氢材料之一，它是开发用于超净H ₂的高效多相催化剂的方法在温和条件下，在不使用任何碱或添加剂的情况下，从FA中生成氟仍然是一个重大挑战。在这里，我们介绍了一种包含三苯胺（TPA）和2,6-双（1,2,3-三唑-4-基）吡啶基（BTP）单元（TB-POP）的多孔有机聚合物。可以使用方便的方法轻松生成平均尺寸为1.5±0.6 nm的超细钯纳米颗粒（NPs），并将其均匀分散在TB-POP载体上。TPA和BTP单元在TB-POP的宿主框架中是均匀排列的；它们可作为碱性位点的有效替代品，将FA质子化为甲酸中间体。Pd @ TB‐POP在FA水溶液的无添加剂脱氢中表现出卓越的催化活性和高选择性。50°C时的初始周转频率（TOF）值高达1344 h ^-1。形成鲜明对比的是，在催化体系中使用甲酸钠作为添加剂会降低催化活性。在FA脱氢过程中有效地固定了超细钯NP，并且连续催化运行后未观察到钯NP的聚集。