Composition-controlled catalysis of reduced graphene oxide supported CuPd alloy nanoparticles in the hydrolytic dehydrogenation of ammonia borane
Composition-controlled catalysis of reduced graphene oxide supported CuPd alloy nanoparticles in the hydrolytic dehydrogenation of ammonia borane
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DOI：
10.1016/j.apcata.2015.01.020
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发表时间：
2015-03-25
影响因子：
5.5
通讯作者：
Metin, Onder
中科院分区：
文献类型：
--
作者：
Gungormez, Kubra;Metin, Onder
本文讨论的是还原氧化石墨烯 (RGO) 上负载的 CuPd 合金纳米颗粒 (NP) 在氨硼烷 (AB) 水解脱氢中的成分控制催化作用。通过使用表面活性剂辅助的有机溶液相方案合成了几乎单分散的 CuPd 合金 NP，该方案包括在 80 ℃ 的油胺和 1-十八碳烯中通过吗啉硼烷络合物共还原 Pd 和 Cu 的乙酰丙酮络合物。所提出的配方使我们能够对 CuPd 合金 NP 进行成分控制。可以制备三种不同成分的CuPd合金NPs（2.7 nm Cu30Pd70、2.9 nm Cu48Pd52、3.0 nm Cu75Pd25），其中Cu75Pd25 NPs在AB水解产氢中表现出最好的催化性能。在针对所制备的 Cu75Pd25 合金纳米颗粒测试的各种载体材料中，RGO-Cu75Pd25 催化剂在 AB 水解中表现出最高的性能。此外，在Ar-H-2（5％H-2）气流下400℃退火1小时后，RGO-Cu75Pd25催化剂的活性得到显着增强，并且在AB室温水解中获得了前所未有的29.9min(-1)的TOP值。这里报道的 TOF 值远高于 RGO-Cu (TOF = 3.61 min(-1))，甚至高于 RGO-Pd 催化剂 (TOF = 26.6 min(-1))。还根据催化剂浓度、底物浓度和温度研究了 RGO-Cu75Pd25 催化 AB 水解的详细动力学。 AB催化水解的表观活化能为45+/-3kJmol(-1)。 (C) 2015 Elsevier B.V. 保留所有权利。
Addressed herein is the composition-controlled catalysis of CuPd alloy nanoparticles (NPs) supported on reduced graphene oxide (RGO) in the hydrolytic dehydrogenation of ammonia borane (AB). Nearly monodisperse CuPd alloy NPs were synthesized by using a surfactant-assisted organic solution phase protocol comprising the co-reduction of acetylacetonate complexes of Pd and Cu by morpholine borane complex in oleylamine and 1-octadecene at 80 degrees C. The presented recipe allowed us to make a composition control over the CuPd alloy NPs. Three different compositions of CuPd alloy NPs (2.7 nm Cu30Pd70, 2.9 nm Cu48Pd52, 3.0 nm Cu75Pd25) could be prepared among which the Cu75Pd25 NPs showed the best catalytic performance in hydrogen generation from the hydrolysis of AB. Among the various support materials tested for as-prepared Cu75Pd25 alloy NPs, the RGO-Cu75Pd25 catalysts showed the highest performance in the hydrolysis of AB. Moreover, the activity of the RGO-Cu75Pd25 catalysts were dramatically enhanced by annealing them at 400 degrees C for 1 h under Ar-H-2 (5% H-2) gas flow and an unprecedented TOP value of 29.9 min(-1) was obtained in the hydrolysis of AB at room temperature. The reported TOF value here is much higher than RGO-Cu (TOF = 3.61 min(-1)) and even higher than RGO-Pd catalysts (TOF = 26.6 min(-1)). The detailed kinetics of RGO-Cu75Pd25 catalyzed AB hydrolysis was also studied depending on catalyst concentration, substrate concentration and temperature. The apparent activation energy of the catalytic hydrolysis of AB was calculated to be 45 +/- 3 kJ mol(-1). (C) 2015 Elsevier B.V. All rights reserved.