Feng Zhaolu, Wang Yindong, Bai Xuefeng
College of Materials Science and Chemical Engineering, Harbin Engineering University, Harbin, 150001, China.
Institute of Petrochemical, Heilongjiang Academy of Sciences, Harbin, 150040, China.
Environ Sci Pollut Res Int. 2022 Jun;29(26):39266-39280. doi: 10.1007/s11356-022-18926-4. Epub 2022 Jan 31.
Dehydrogenation reactions are critical in hydrogen storage based on a liquid organic hydrogen carrier (LOHC) system. Speeding up the dehydrogenation rate and lowering the reaction temperature are the main focuses of LOHC dehydrogenation catalysts. In this paper, Pd/SBA-15 catalysts (Pd-IP/S15) were prepared by NaOH treatment of surface hydroxyl groups on SBA-15, the ion exchange of Na with Pd(NH), and then reduction of Pd ions via glow discharge plasma. The dehydrogenation performance of dodecahydro-N-ethylcarbazole on the prepared catalysts is studied. The turnover frequency of Pd-IP/S15 is 13.94 min at 170°C, which is 10.25 times that of commercial Pd/C. It is ensured via the ion exchange method that Pd(NH) could be precisely targeted at the Si-OH of SBA-15 to form Si-O-Pd(NH), which effectively prevents the aggregation and uncontrollable growth of Pd nanoparticles (NPs) during the in situ reduction by plasma. Pd NPs with high dispersion are obtained on SBA-15, which enhances the catalytic activity of Pd-IP/S15. The coordination of Pd NPs with O of Si-OH on SBA-15 enabled Pd-IP/S15 to exhibit excellent catalytic stability. After 7 dehydrogenation cycles at 180°C, the dehydrogenation efficiency remained above 97%.
脱氢反应在基于液态有机氢载体（LOHC）系统的氢储存中至关重要。加快脱氢速率并降低反应温度是LOHC脱氢催化剂的主要研究重点。本文通过对SBA-15表面羟基进行NaOH处理、Na与Pd(NH)进行离子交换，然后通过辉光放电等离子体还原Pd离子来制备Pd/SBA-15催化剂（Pd-IP/S15）。研究了制备的催化剂上十二氢-N-乙基咔唑的脱氢性能。在170°C下，Pd-IP/S15的周转频率为13.94 min⁻¹，是商业Pd/C的10.25倍。通过离子交换法确保Pd(NH)能够精确地靶向SBA-15的Si-OH，形成Si-O-Pd(NH)，这有效地防止了等离子体原位还原过程中Pd纳米颗粒（NPs）的聚集和不可控生长。在SBA-15上获得了高分散的Pd NPs，这提高了Pd-IP/S15的催化活性。Pd NPs与SBA-15上Si-OH的O配位使Pd-IP/S15表现出优异的催化稳定性。在180°C下进行7次脱氢循环后，脱氢效率仍保持在97%以上。
