Excellent Pd supported on carbon catalysts for the dehydrogenation of formic acid were synthesized from a lignocellulosic biomass residue. The preparation of the carbon support consisted of a H₃PO₄-assisted hydrothermal carbonization (HTC) and activation of a hemp residue and subsequent nitrogen functionalization. It was observed that the presence of nitrogen groups influenced both the size and the electronic properties of the Pd nanoparticles, which ultimately affected their catalytic properties. Furthermore, the catalytic performance also depended on the synthesis conditions used in the preparation of the catalysts (i.e., reduction of the Pd nanoparticles with NaBH₄ prior to the catalytic test or in situ reduction). The best-performance catalysts (Pd/N-HTC (n.r.)), which were prepared by in situ reduction of the nanoparticles, displayed a remarkable catalytic activity with a very high TOF number of 8365 h^–1 (TOF value calculated for the 2nd catalytic run and expressed per surface Pd atom) and outstanding stability during 6 consecutive reaction cycles, although the initial activity is maintained for 12 cycles. The catalytic system studied is among the most stable ever reported Pd-based heterogeneous catalysts for the dehydrogenation of formic acid.

中文翻译：

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从生物质废料制备高稳定性的氮掺杂碳载钯基催化剂，用于从甲酸生产H ₂

从木质纤维素生物质残渣合成了负载在碳催化剂上用于甲酸脱氢的优良钯。碳载体的制备由H ₃ PO ₄辅助的水热碳化（HTC）和大麻残基的活化以及随后的氮官能化组成。观察到氮基团的存在影响钯纳米颗粒的尺寸和电子性能，最终影响其催化性能。此外，催化性能还取决于用于制备催化剂的合成条件（即用NaBH ₄还原Pd纳米颗粒）在进行催化测试或原位还原之前）。通过纳米粒子的原位还原制备的性能最佳的催化剂（Pd / N-HTC（nr））显示出显着的催化活性，TOF值为8365 h ^–1（第二次计算的TOF值）尽管最初的活性保持了12个循环，但在连续6个反应循环中仍具有出色的稳定性。研究的催化系统是有史以来最稳定的用于甲酸脱氢的基于Pd的非均相催化剂。