Preparation of Rh/N-GMCs nanocatalyst and its catalytic performance for the hydrolytic dehydrogenation of ammonia borane
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摘要:
本实验通过高温焙烧三聚氰胺和葡萄糖混合物制备出具有独特层状结构的氮掺杂石墨相炭材料(N-GMCs)。再以N-GMCs为载体采用浸渍-还原法将金属Rh负载到载体表面,最终制得Rh/N-GMCs催化剂。结果表明,Rh与N-GMCs之间存在强的金属-载体相互作用,Rh的负载量为0.4%时,反应转化频率(TOF)值达到峰值,此时0.4%Rh/N-GMCs催化剂的TOF为645.3 min–1,该催化剂上氨硼烷水解的活化能(Ea)为54.0 kJ/mol,氨硼烷脱氢速率随氨硼烷浓度和催化剂浓度呈现正相关,该催化剂循环10次之后,催化活性未明显下降,表明该催化剂具有较好的循环稳定性。
Abstract:In this paper, nitrogen-doped graphitic carbon materials (N-GMCs) with unique layered structure were prepared by calcining a mixture of melamine and glucose at high temperature. The Rh/N-GMCs catalyst was finally prepared by impregnation-reduction method using N-GMCs as the carrier to support the metal Rh on the surface of the carrier. The results showed that there was a strong metal-support interaction between Rh and N-GMCs, and the reaction transition frequency (TOF) value reached a peak when the loading amount of Rh was 0.4%. At this time, the TOF value of AB dehydrogenation reaction catalyzed by 0.4%Rh/N-GMCs catalyst was 645.3 min–1, and the activation energy (Ea) of ammonia borane hydrolysis on this catalyst was 54.0 kJ/mol. The rate was positively correlated with the ammonia borane concentration and the catalyst concentration. After 10 cycles of the catalyst, the catalytic activity did not decrease significantly, indicating that the catalyst had excellent cyclic stability.
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图 6 (a) 不同Rh负载量的Rh/N-GMCs催化剂在283 K催化AB水解反应中的脱氢速率;(b) 脱氢速率与Rh负载量的对数值;(c) AB的转化率随Rh负载量的变化;(d) 不同Rh负载量的Rh/N-GMCs催化剂在283 K脱氢AB所对应的TOF值
Figure 6 (a) Plots of hydrogen evolution rate for the hydrolysis of AB with different rhodium concentration at 283 K; (b) logarithmic plot of hydrogen evolution rate versus Rh loading; (c) conversion rate of AB for the dehydrogenation of AB at different rhodium concentration; (d) turnover frequency (TOF) values for the dehydrogenation of AB at 283 K when Rh/N-GMCs with different rhodium loading
表 1 室温下水溶液中AB水解制氢各种贵金属催化剂的催化活性
Table 1 Catalytic activities of various noble metal catalysts for AB hydrolysis in aqueous solution at room temperature
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