Preparation of graphene-supported Co-CeOx nanocomposites as a catalyst for the hydrolytic dehydrogenation of ammonia borane
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摘要: 高效、低成本催化剂是实现以氨硼烷(NH3BH3, AB)为化学储氢材料水解产氢的关键。本文采用简单的浸渍还原法,制备了石墨烯负载的Co-CeOx 纳米复合物(Co-CeOx /graphene)催化剂,对其氨硼烷水解产氢的催化性能进行了研究。结果表明,Co与CeOx 之间存在强的协同电子效应,同时高分散的纳米Co-CeOx 粒子与石墨烯之间存在强的金属--载体相互作用,因而所制备的Co-CeOx /graphene催化剂对氨硼烷水解具有良好的催化活性和循环稳定性。Co-CeOx /graphene催化剂上氨硼烷水解的活化能( Ea )为39.5 kJ/mol,反应转化频率(TOF)为45.1 min−1,分别为纯Co及Co/graphene催化剂上的12倍与9倍之多,高于大多数已报道的非贵金属催化剂。Abstract: Low-cost and high-performance catalyst is crucial for hydrogen generation via the hydrolysis of ammonia borane (NH3BH3, AB) as a chemical hydrogen storage material. In this work, Co-CeOx nanocomposites supported on graphene (Co-CeOx/graphene) were prepared through a facile impregnation and chemical reduction method and used as a catalyst in the hydrolytic dehydrogenation of ammonia borane. The results indicate that the as-prepared Co-CeOx/graphene nanocomposite exhibits superior catalytic activity and recycling stability in the hydrolysis of ammonia borane, owing to the ultra-fine size of Co-CeOx particles, the strong synergistic electronic effect between Co and CeOx, as well as the strong metal-support interaction between Co-CeOx and graphene. For the hydrolysis of ammonia borane over the optimized Co-CeOx/graphene catalyst, the turnover frequency (TOF) reaches 45.1 min−1, with the activation energy (Ea) of 39.5 kJ/mol; such a TOF value is 12 times and 9 times higher than those over Co and Co/graphene, respectively, also much higher than those reported for most noble-metal-free catalysts.
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Key words:
- hydrolytic dehydrogenation /
- ammonia borane /
- catalyst /
- Co-CeOx /
- graphene
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图 6 Co-CeOx/graphene催化剂在298 K下催化氢硼烷水溶液(200 mmol/L, 5 mL)释放氢的生产率与反应时间的关系(Co/AB = 0.05, Ce = 45%);插图显示了Co-CeOx/graphene在不同的Ce含量下催化AB水解脱氢的反应时间
Figure 6 Hydrogen productivity vs. reaction time forhydrolysis of aqueous ammonia borane(200 mmol/L, 5 mL) catalyzed by the Co-CeOx/graphene catalyst at 298 K (Co/AB = 0.05, Ce = 45%); the inset shows the reaction time for the hydrolytic dehydrogenation of AB catalyzed by Co-CeOx/graphene with different molar contents of CeOx
图 7 不同稀土元素的Co-ReOx/graphene催化剂催化氢硼烷水溶液(200 mmol/L, 5 mL)释放氢的生产率与反应时间的关系(Co/AB = 0.05, Re = Ce、La、Tb、Er、Dy and Yb, 45% of Re)
Figure 7 Hydrogen generation from the hydrolysis of ammonia borane (200 mmol/L, 5 mL) catalyzed by Co-ReOx /graphene (Re = Ce, La, Tb, Er, Dy and Yb, 45% of Re) under ambient atmosphere at room temperature (Co/AB = 0.05)
图 9 (a) Co-CeOx/graphene, (b) Co/graphene, (c) Co催化剂在298−313 K下催化氨硼烷溶液(5 mmol/L, 5 mL)放氢量与时间的关系(Co/AB = 0.05, Ce = 45%);(d), (e), (f)分别为(a), (b), (c)对应的阿伦尼乌斯曲线图
Figure 9 Evolution plots of hydrogen generated vs. time for the hydrolysis of ammonia borane (200 mmol/L, 5 mL, Co/AB=0.05) catalyzed by Co-CeOx /graphene (Ce = 45%) (a), Co/graphene (b) and Co (c) at different temperatures (298–313 K); Graphs (d), (e) and (f) are the Arrhenius plots obtained from the Graphs (a), (b) and (c), respectively
表 1 室温下水溶液中AB水解制氢各种非贵金属催化剂的催化活性
Table 1 Catalytic performances of various non-noble metal catalysts for hydrogen generation from the hydrolysis of aqueous AB at room temperature
Catalyst TOF/
$({{\bf{mo} }{ {\bf{l} }_{ { {\rm{H} }_{_2} } } }\cdot{\bf{mol} }_{ {\bf{metal} } }^{\bf{ - 1}}\cdot{\bf{mi} }{ {\bf{n} }^{\bf{ - 1}} }} )$Ea/
(kJ·mol−1)Ref. Co/MIL-101-1-U 51.4 31.3 [34] CoNi/RGO 19.5 39.9 [22] Ag@CoNi/graphene 99.3 36.15 [35] Co-(CeOx)0.91/NGH 79.5 31.82 [36] Co/graphene 13.80 32.75 [37] Ag@Co/graphene 102.4 20.03 [38] Ag@Ni /graphene 77 49.56 [38] Cu@CoNi/graphene 15.46 58.41 [39] Co0.75B0.25 7.24 40.85 [40] Co0/CeO2 7.0 43 [33] Ni-CeOx/graphene 68.2 28.9 [41] Co/γ-Al2O3 2.3 62 [42] Co-CeOx/graphene 45.1 39.5 this work Co/graphene 4.75 58.0 this work Co 3.68 70.3 this work -
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