Xue Zhiwei, Shen Yuesong, Li Peiwen, Zhang Yu, Li Junjie, Qin Bin, Zhang Jin, Zeng Yanwei, Zhu Shemin
College of Materials Science and Engineering, Jiangsu Collaborative Innovation Center for Advanced Inorganic Function Composites, Jiangsu National Synergetic Innovation Center for Advanced Materials, Nanjing Tech University, Nanjing, 210009, P. R. China.
Department of Aerospace and Mechanical Engineering, The University of Arizona, Tucson, AZ, 85721, USA.
Small. 2018 Aug;14(34):e1800927. doi: 10.1002/smll.201800927. Epub 2018 Jul 20.
The hydrogen economy is accelerating technological evolutions toward highly efficient hydrogen production. In this work, the catalytic performance of NiO/NaCl for hydrogen production via autothermal reforming of ethyl acetate and water is further improved through lanthanum modification, and the resulted 3%-NiLaO /NaCl catalyst achieves as high as 93% H selectivity and long-term stability at 600 °C. The promoting effect is caused by the strong interactions between lanthanum and NiO/NaCl, by which LaNiO and a novel LaOCl phase are formed. The key role of LaOCl in promoting low-temperature hydrogen production is highlighted, while effects of LaNiO are well known. The LaOCl (010) facet possesses high adsorption capacity toward co-chemisorbing ethyl acetate and water. LaOCl strongly interacts with ethyl acetate and H O in the form of hydrogen bonding and coordination effect. The interactions induce tensions inside ethyl acetate and H O, activate the molecules, and hence decrease the energy barrier for reaction. In situ Fourier transform infrared spectroscopy (FTIR) reveals that LaOCl along with NaCl enhances the adsorption ability of NiO/NaCl. Moreover, LaOCl improves the dispersion of Ni species in NiO-LaNiO -LaOCl nanosheets, which possess abundant active sites. The effects together promote hydrogen evolution. Furthermore, the NiLaO /NaCl catalyst can be easily reborn after deactivation due to the water solubility of NaCl.
氢经济正在加速推动向高效制氢的技术演进。在这项工作中,通过镧改性进一步提高了NiO/NaCl用于乙酸乙酯和水自热重整制氢的催化性能,所得的3%-NiLaO/NaCl催化剂在600℃时实现了高达93%的H选择性和长期稳定性。促进作用是由镧与NiO/NaCl之间的强相互作用引起的,由此形成了LaNiO和一种新型的LaOCl相。突出了LaOCl在促进低温制氢中的关键作用,而LaNiO的作用是众所周知的。LaOCl(010)晶面对共化学吸附的乙酸乙酯和水具有高吸附能力。LaOCl以氢键和配位作用的形式与乙酸乙酯和H₂O强烈相互作用。这些相互作用在乙酸乙酯和H₂O内部产生张力,激活分子,从而降低反应的能量壁垒。原位傅里叶变换红外光谱(FTIR)表明,LaOCl与NaCl一起增强了NiO/NaCl的吸附能力。此外,LaOCl改善了Ni物种在具有丰富活性位点的NiO-LaNiO-LaOCl纳米片中的分散性。这些效应共同促进了析氢。此外,由于NaCl的水溶性,NiLaO/NaCl催化剂失活后可易于再生。