微米级棒状氧化铝团簇体的合成及表征

doi:10.16085/j.issn.1000-6613.2019-1016

摘要/Abstract

摘要：

以γ-Al₂O₃粉末及碳酸氢铵为原料，采用水热技术成功制备微米级棒状氧化铝团簇体，考察反应温度、反应时间、物料配比等因素对微米级棒状氧化铝团簇体形貌的影响，并应用XRD、NMR、TEM、FTIR、SEM、N₂吸附-脱附、吡啶吸附-脱附等技术分析其物化性质及结构。结果表明：当γ-Al₂O₃粉末与碳酸氢铵质量比为 1∶1.75、反应温度为140℃、反应时间为6h时，合成的微米级棒状氧化铝团簇体直径为5～15μm，该微米级棒状氧化铝团簇体由直径50～100nm、长0.5～3μm的棒状氧化铝交叉堆积而成，比表面积为300m²/g、孔容为0.67mL/g，具有双重孔分布，可几孔径分别为3.5nm和26nm，表面同时含有六配位铝离子、五配位铝离子和四配位铝离子。

关键词: 氧化铝, 团簇体, 合成, 表征

Abstract:

Micron rod-like alumina clusters were successfully prepared from γ-Al₂O₃ powder and ammonium bicarbonate by hydrothermal method. The effects of reaction temperature, reaction time and material ratio on the morphology of rod-like alumina clusters were investigated. The physicochemical properties and structures of rod-like alumina clusters were analyzed by XRD, NMR, TEM, FTIR, SEM, N₂ adsorption-desorption and pyridine adsorption-desorption techniques. The results showed that the mass ratio of γ-Al₂O₃ powder to ammonium bicarbonate was 1∶1.75, the reaction temperature was 140℃, the reaction time was 6h and the diameter of the synthesized micron grade rod-like alumina clusters was 5—15μm. The micron-grade rod-like alumina cluster was formed by cross-stacking of rod-like alumina with a diameter of 50—100nm and a length of 0.5—3μm. The specific surface area was 300m²/g and pore volume was 0.67mL/g with dual pore distribution. The pore sizes were 3.5nm and 26nm, respectively. It also contained six coordination aluminum ions, five coordination aluminum ions and four coordination aluminum ions.

Key words: alumina, cluster, synthesis, characterization

中图分类号:

TQ 426.5

季洪海,凌凤香,张会成,王少军,沈智奇. 微米级棒状氧化铝团簇体的合成及表征[J]. 化工进展, 2020, 39(3): 1108-1114.

Honghai JI,Fengxiang LING,Huicheng ZHANG,Shaojun WANG,Zhiqi SHEN. Synthesis and characterization of micron rod-like alumina clusters[J]. Chemical Industry and Engineering Progress, 2020, 39(3): 1108-1114.

图/表 9

图1 反应温度对微米级棒状氧化铝团簇体形貌（SEM）的影响

图2 反应时间对微米级棒状氧化铝团簇体形貌（SEM）的影响

图3 物料配比对微米级棒状氧化铝团簇体形貌（SEM）的影响

图4 微米级棒状氧化铝团簇样品的XRD谱图

图5 处理前后样品氮气吸附-脱附及孔分布曲线

图6 微米级棒状氧化铝团簇体样品FTIR谱

图7 吡啶吸附原位红外光谱图

图8 微米级棒状氧化铝团簇体样品NMR表征

图9 微米级棒状氧化铝团簇体样品TEM表征

参考文献 21

1	MONICA T,STEFANO P T.γ-Alumina as a support for catalysts: a review of fundamental aspects[J].Eur. J. Inorg. Chem.,2005,17:3393-3403.
2	BARTHOMEW C H,FARRAUTO R J.Fundamentals of industrial catalytic processes[M].2nd. Hoboken:Wiley,2005:3-59.
3	XIA Y,YANG P,SUN Y,et al.One-dimensional nanostructures:synthesis, characterization, and applications[J].Advanced Materials,2003,15(5):353-389.
4	CHEN X Y,ZHANG Z J,LI X L,et al.Controlled hydrothermal synthesis of colloidal boehmite (γ-AlOOH) nanorods and nanoflakes and their conversion intoγ-Al₂O₃ nanocrystals[J].Solid State Communications,2008,145(7):368-373.
5	HOU H W,XIE Y,YANG Q,et al.Preparation and characterization of γ-AlOOH nanotubes and nanorods[J].Nanotechnology,2005,16(6):19-25.
6	LIU X,LI X,YAN Z.Facile route to prepare bimodal mesoporous γ-Al₂O₃ as support for highly active CoMo-based hydrodesulfurization catalyst[J].Applied Catalysis B: Environmental, 2012,121/122(13):50-56.
7	LI G,LU X,TANG Z,et al.Preparation of NiMo/γ-Al₂O₃ catalysts with large pore size for vacuum residue hydrotreatment[J].Materials Research Bulletin,2013,48(11):4526-4530.
8	CAI W Q,ZHUO J L,FANG J M,et al.2-Ethyl-9,10-anthraquinone assisted sol-gel synthesis of Pd/γ-Al₂O₃nanorods with enhanced catalytic performance in 2-ethyl-9,10-anthraquinone hydrogenation[J].Chinese Journal of Chemical Engineering,2019,1(3):1-7.
9	GAO X Q,LU W D,LU A H,et al.Rod-shaped porous alumina-supported Cr₂O₃ catalyst with low acidity for propane dehydrogenation[J].Chinese Journal of Chemical Engineering,2019,40(2):184-191.
10	CAI W Q,HU Y Z,CHEN J,et al.Synthesis of nanorods-like mesoporous γ-Al₂O₃ with enhanced affinity towards Congo red removal: effects of anions and structure-directing agents[J].Cryst. Eng. Comm.,2012,14:972-977.
11	李志强.重油转化——21世纪石油炼制技术的焦点[J].炼油设计,1999,29(12):8-14.
	LI Z Q.Heaby oil upgrading——A focus of petroleum refining techniques in 21st century[J].Petroleum Refinery Engineering,1999,29(12):8-14.
12	ABSIHABI M,STANISLOUS A,ALMUGHNI T,et al.Hydroprocessing of vacuum residues, relation between catalyst activity, deactivation and pore size distribution[J].Fuel,1995,74(8):1211-1215.
13	辛勤,罗梦飞.现代催化研究方法[M].北京:科学出版社,2009:15-23.
	XIN Q,LUO M F.Modern catalytic research methods[M].Beijing:Science Press,2009:15-23.
14	DINGE M,AUTET P,RAYBAUD P,et al.Use of DFT to achieve a rational understanding of acid-basic properties of γ-alumina surfaces[J].J. Catal.,2004,226(1):54-68.
15	张涛,臧璟龄,胡爱华,等.锂对于γ-Al₂O₃表面酸中心的调变作用及其积炭性能的影响[J].催化学报,1990,11 (5):341-347.
	ZHANG T,ZANG J L,HU A H,et al.Effect of lithium on the acidic property of γ-Al₂O₃ and its carbon deposition[J].Chinese Journal of Catalysis,1990,11(5):341-347.
16	唐国旗,张春富,孙长山,等.活性氧化铝载体的研究进展[J].化工进展,2011,30(8):1756-1765.
	TANG G Q,ZHANG C F,SUN C S,et al.Research progress of γ-alumina support[J].Chemical Industry and Engineering Progress,2011,30(8):1756-1765.
17	PARRY E P.An infrared study of pyridine adsorbed on acidic solids. Characterization of surface acidity[J].J. Catal.,1963,2(5):371-379.
18	CORMA A,FORNES V,ORTEGE E.The nature of acid sites on fluorinated γ-Al₂O₃[J].J. Catal.,1985,92(2):284-290.
19	HUGGINS B A,ELLIS P D.Aluminum-27 nuclear magnetic resonance study of aluminas and their surfaces[J].Journal of the American Chemical Society,1992,114(6):2098-2108.
20	TSYGANENKO A A,MARDILOVICH P P.Structure of alumina surfaces[J].Journal of the Chemical Society,Faraday Transactions,1996,92(23):4843-4852.
21	SAKASHITA Y,ARAKI Y,SHIMADA H.Effects of surface orientation of alumina supports on the catalytic functionality of molybdenum sulfides[J].Appl. Catal. A,2001,15:101-110.

[1]	时永兴, 林刚, 孙晓航, 蒋韦庚, 乔大伟, 颜彬航. 二氧化碳加氢制甲醇过程中铜基催化剂活性位点研究进展[J]. 化工进展, 2023, 42(S1): 287-298.
[2]	杨霞珍, 彭伊凡, 刘化章, 霍超. 熔铁催化剂活性相的调控及其费托反应性能[J]. 化工进展, 2023, 42(S1): 310-318.
[3]	赵巍, 赵德银, 李世瀚, 刘洪达, 孙进, 郭艳秋. 三嗪型天然气管道缓蚀型减阻剂合成与应用[J]. 化工进展, 2023, 42(S1): 391-399.
[4]	王正坤, 黎四芳. 双子表面活性剂癸炔二醇的绿色合成[J]. 化工进展, 2023, 42(S1): 400-410.
[5]	向阳, 黄寻, 魏子栋. 电催化有机合成反应的活性和选择性调控研究进展[J]. 化工进展, 2023, 42(8): 4005-4014.
[6]	陆洋, 周劲松, 周启昕, 王瑭, 刘壮, 李博昊, 周灵涛. CeO₂/TiO₂吸附剂煤气脱汞产物的浸出规律[J]. 化工进展, 2023, 42(7): 3875-3883.
[7]	鲁少杰, 刘佳, 冀芊竹, 李萍, 韩月阳, 陶敏, 梁文俊. 硅藻土基复合填料制备及滴滤塔去除二甲苯的性能[J]. 化工进展, 2023, 42(7): 3884-3892.
[8]	于志庆, 黄文斌, 王晓晗, 邓开鑫, 魏强, 周亚松, 姜鹏. B掺杂Al₂O₃@C负载CoMo型加氢脱硫催化剂性能[J]. 化工进展, 2023, 42(7): 3550-3560.
[9]	王帅旗, 王从新, 王学林, 田志坚. 无溶剂快速合成ZSM-12分子筛[J]. 化工进展, 2023, 42(7): 3561-3571.
[10]	余希希, 张金帅, 雷文, 刘承果. 基于动态共价键自修复的光固化高分子材料研究进展[J]. 化工进展, 2023, 42(7): 3589-3599.
[11]	王知彩, 刘伟伟, 周璁, 潘春秀, 闫洪雷, 李占库, 颜井冲, 任世彪, 雷智平, 水恒福. 基于煤基腐殖酸的高效减水剂合成与性能表征[J]. 化工进展, 2023, 42(7): 3634-3642.
[12]	陈森, 殷鹏远, 杨证禄, 莫一鸣, 崔希利, 锁显, 邢华斌. 功能固体材料智能合成研究进展[J]. 化工进展, 2023, 42(7): 3340-3348.
[13]	刘宇龙, 姚俊虎, 舒闯闯, 佘跃惠. 磁性Fe₃O₄纳米颗粒的生物合成及其在提高采收率中的应用[J]. 化工进展, 2023, 42(5): 2464-2474.
[14]	郭朋举, 何小波, 银凤翔. 电催化氮还原合成氨MOF基催化剂研究进展[J]. 化工进展, 2023, 42(4): 1797-1810.
[15]	王嘉, 彭冲, 唐磊, 陆安慧. 渣油加氢催化剂活性相结构调控及对反应性能影响[J]. 化工进展, 2023, 42(4): 1811-1821.