Gold supported on zirconia polymorphs for hydrogen generation from formic acid in base-free aqueous medium
Gold supported on zirconia polymorphs for hydrogen generation from formic acid in base-free aqueous medium
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氧化锆多晶型物负载金用于在无碱水介质中从甲酸产生氢气
DOI：
10.1016/j.jpowsour.2016.08.056
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发表时间：
2016-10-01
影响因子：
9.2
通讯作者：
Cao, Yong
中科院分区：
文献类型：
--
作者：
Bi, Qing-Yuan;Lin, Jian-Dong;Cao, Yong
甲酸（FA）作为一种安全、方便的可再生能源转化储氢材料受到了广泛关注。然而，开发一种有效的非均相催化剂，用于在温和条件下在不存在任何碱或添加剂的情况下选择性分解超净H-2气体的FA仍然是一个重大挑战。基于我们以前的工作，Au/ZrO 2作为一个强大的和有效的催化剂，在胺体系中的FA脱氢，我们在这里报告的负载Au纳米粒子可以实现在无碱的水介质中的FA脱氢接近完成。非常重要的是，对于Au/m-ZrO 2，在80 ℃下，在开放系统中可以容易地获得高达81.8 L H-2 g（Au）（-1）h（-1）的优异速率，在封闭系统中可以容易地获得5.9 MPa的高压气体。原位漫反射红外傅里叶变换（DRIFT）和CO2程序升温脱附（TPD）技术表明，Au/m-ZrO 2比Au/t-ZrO 2和Au/a-ZrO 2具有更高的表面碱性位密度。表面的碱性位能显著地促进关键的FA去质子化过程，这似乎是获得高脱氢活性的关键因素。通过动力学同位素效应实验，观察到了溶剂H_2O与FA底物之间的H/D交换。(C)2016爱思唯尔B. V.保留所有权利。
Formic acid (FA) has attracted considerable attention as a safe and convenient hydrogen storage material for renewable energy transformation. However, development of an efficient heterogeneous catalyst for selective FA decomposition for ultraclean H-2 gas in the absence of any alkalis or additives under mild conditions remains a major challenge. Based on our previous work on Au/ZrO2 as a robust and efficient catalyst for FA dehydrogenation in amine system, we report here ZrO2 with different nanocrystal poly morphs supported Au nanoparticles can achieve near completion of FA dehydrogenation in base-free aqueous medium. Of significant importance is that an excellent rate of up to 81.8 L H-2 g(Au)(-1) h(-1) in open system and highly pressurized gas of 5.9 MPa in closed one can be readily attained at 80 degrees C for Au/m-ZrO2. In situ diffuse reflectance infrared Fourier transform (DRIFT) and CO2-temperature programmed desorption (TPD) techniques revealed that Au/m-ZrO2 exhibits a higher density of surface basic sites than Au/t-ZrO2 and Au/a-ZrO2. Basic sites in surface can substantially facilitate crucial FA deprotonation process which appears to be a key factor for achieving high dehydrogenation activity. The H/D exchange between solvent of H2O and substrate of FA was observed by the kinetic isotope effect experiments. (C) 2016 Elsevier B.V. All rights reserved.