镍纳米粒子耦合氧空位高效催化转化棕榈酸制备烷烃  

Ni nanoparticle coupled surface oxygen vacancies for efficient synergistic conversion of palmitic acid into alkanes

作　　者：曾严 王慧[2] 杨惠茹 隽超 李丹 温晓东[2] 张帆 邹吉军[3] 彭冲 胡常伟[1] Yan Zeng;Hui Wang;Huiru Yang;Chao Juan;Dan Li;Xiaodong Wen;Fan Zhang;Ji‐Jun Zou;Chong Peng;Changwei Hu(Key Laboratory of Green Chemistry and Technology,Ministry of Education,College of Chemistry,Sichuan University,Chengdu 610064,Sichuan,China;State Key Laboratory of Coal Conversion,Institute of Coal Chemistry,Chinese Academy of Sciences,Taiyuan 030001,Shanxi,China;Key Laboratory for Green Chemical Technology of the Ministry of Education,School of Chemical Engineering and Technology,Tianjin University,Tianjin 300072,China;State Key Laboratory of Fine Chemicals,School of Chemical Engineering,Dalian University of Technology,Dalian 116024,Liaoning,China)

机构地区：[1]四川大学化学学院教育部绿色化学与技术重点实验室,四川成都610064 [2]中国科学院山西煤炭化学研究所煤转化国家重点实验室,山西太原030001 [3]天津大学化工学院,天津300350 [4]大连理工大学化工学院,辽宁大连116024

出　　处：《Chinese Journal of Catalysis》2023年第4期229-242,共14页催化学报（英文）

基　　金：国家自然科学基金(21972099);四川省应用基金项目(2021YJ0305);111项目(B17030).

摘　　要：随着能源需求的增加和生态环境的恶化,可再生资源的开发与利用越来越受到人们的重视.其中,生物质能源分布广泛,储量丰富,是化石燃料的理想替代品.然而生物质具有高含氧量、高粘度和低热值等特性,开发高效的加氢脱氧催化剂对生物质资源的开发和利用具有重要的应用价值.近年来,研究者们对生物质(脂肪酸及其衍生物)加氢脱氧催化体系进行了大量研究,发现Ni/CeO_(2)基催化剂能够有效地催化生物质转化并获得较高的生物油产率,然而CeO_(2)载体的氧空位含量与Ni纳米颗粒尺寸、催化剂脱氧性能之间的关系仍然不明晰.本文采用水热合成法和沉淀法分别制备了H-CeO_(2)和P-CeO_(2)载体(商用CeO_(2)标记为C-CeO_(2)),通过浸渍法制备了Ni/H-CeO_(2),Ni/P-CeO_(2)和Ni/C-CeO_(2)催化剂,同时采用无氧空位的SiO_(2)做载体制备了Ni/SiO_(2)催化剂,研究了CeO_(2)氧空位含量对Ni纳米粒子尺寸的影响及其与加氢脱氧催化性能之间的关系.EPR结果表明,不同载体上氧空位含量的顺序为H-CeO_(2)>P-CeO_(2)>C-CeO_(2).XRD结果表明,在H-CeO_(2)载体上生成的Ni纳米粒子尺寸最小,分散度最高;在C-CeO_(2)载体上生成的Ni纳米粒子尺寸最大,分散度最差;而在无氧空位的SiO_(2)载体上生成的Ni纳米粒子尺寸明显大于H-CeO_(2)和P-CeO_(2)载体上生成的Ni纳米粒子.XPS结果显示,不同载体上的O表面/(O表面+O晶格)的比值顺序为H-CeO_(2)>P-CeO_(2)>C-CeO_(2),表明H-CeO_(2)载体上具有最高的氧空位含量,C-CeO_(2)载体上氧空位含量最低,与EPR结果一致;Ni/H-CeO_(2),Ni/P-CeO_(2)和Ni/C-CeO_(2)催化剂上氧空位含量顺序与载体一致,但其氧空位含量比纯载体高,说明Ni有利于氧空位的生成.Raman结果表明,Ni/H-CeO_(2)催化剂上具有的氧空位含量最高,Ni/P-CeO_(2)次之,Ni/C-CeO_(2)最差,与XPS结果一致.H2-TPR结果表明,氧空位的存在增强了Ni与CeO_(2)载体的相互作用,有利于Ni的�The catalytic transformation of renewable biomass oil(mainly comprising fatty acids and triglycerides)into high‐value alkanes is a versatile technique,and Ni‐based catalysts are considered to be the most suitable substitutes for precious metals.Ni nanoparticles supported on CeO_(2)carriers,prepared by hydrothermal synthesis(Ni/H‐CeO_(2))with abundant oxygen vacancies,exhibited superior catalytic activity compared to precious metal catalysts.For the hydrodeoxygenation of palmitic acid,the Ni/H‐CeO_(2)catalyst converted palmitic acid into pentadecane with a 94.8%selectivity under mild reaction conditions.The outstanding catalytic performance of Ni/H‐CeO_(2)can be attributed to the synergistic effect between the Ni nanoparticles for activating hydrogen and the abundant oxygen vacancies for adsorbing oxygen from palmitic acid.The abundant oxygen vacancies of Ni/H‐CeO_(2)improved the interaction between the Ni metal and CeO_(2)support,as confirmed by density functional theory calculations.Therefore,the abundant oxygen vacancies were more conducive to the dispersion of Ni,resulting in the formation of Ni nanoparticles,which enhanced the potential for hydrogen activation due to the increased number of exposed Ni and electronic effects.The high pentadecane selectivity was governed by small Ni nanoparticles.This study provides a novel strategy to obtain an efficient hydrodeoxygenation catalyst for converting biomass oil into biofuel.

关 键 词：加氢脱氧 氧空位 Ni纳米粒子 棕榈酸转化 生物燃料 

分 类 号：TK6[动力工程及工程热物理—生物能] O623.11[理学—有机化学] O643.36[理学—化学]