纳米镍粉的固相合成及其催化性能研究
摘要
一、催化剂的制备及表征
固相法制备纳米Ni粉:以NiSO_4·6H_2O和NaOH为原料,首先采用室温固相法制备纳米Ni(OH)_2粉,经过95%乙醇和蒸馏水交替洗涤去除其中的Na+、SO42-等杂质离子,得到草绿色粉末;粉末再经过110℃烘干8h,350℃焙烧4h、得到黑色粉末纳米NiO;NiO在加热炉中通入氢气还原,400℃还原4h得到灰黑色纳米Ni粉。以NiO为载体采用浸渍法分别掺杂不同含量的Pd、Pt等贵金属对此催化剂进行改性,制得Pd/Ni、Pt/Ni催化剂。采用XRD、TEM、SEM、IR、XPS、BET等手段对催化剂进行了表征。结果表明制备的纳米Ni粉为结构稳定、纯度高、粒径分布均匀的纳米颗粒,平均粒径在20-25nm;掺杂贵金属Pd、Pt后,产物的结构没有发生明显的变化,只是粒径有所增大。所制得的催化剂在空气中均能稳定存放,不易失活,并且在催化剂使用过程中仍保持结构完整。以硝基苯、肉桂醛、马来酸酐等物质的加氢反应为探针实验考察了催化剂的活性。实验发现,纳米Ni粉在硝基苯催化加氢反应中表现出很好的活性,在相同的条件下与Raney-Ni相比,纳米Ni粉具有更好的加氢效果,在工业生产中具有广阔的应用前景。在肉桂醛催化加氢反应中,贵金属Pd对催化剂的改性效果远比贵金属Pt优越。马来酸酐的转化率和选择性都很高,丁二酸酐的收率高达98.7%
二、硝基苯催化加氢性能研究
以硝基苯加氢制备苯胺为探针反应,考察了纳米Ni粉及掺杂贵金属Pd、Pt催化剂的加氢性能,并在相同条件下与Raney-Ni做了比较;同时考察了反应温度、催化剂用量、氢气压力等因素对催化剂反应活性的影响。结果发现,120℃、催化剂用量在～4%,对硝基苯加氢反应有利;同时还发现氢气压力对硝基苯转化率有明显的影响,在催化剂用量为2.0%,120℃反应10h,氢气压力为0.8MPa条件下,硝基苯转化率高达76.42%,苯胺的选择性为100%;在相同的条件下,纳米Ni粉作为催化剂,硝基苯加氢的转化率选择性和选择性比Raney-Ni优越的多,硝基
1. Preparation and characterization of catalysts
Nickel (NiO) powders with the sizes in the range of 20–25 nm were prepared via the reduction of nanosized NiO powders (The nanosized NiO powders were derived from low temperature (350℃) calcinations in air of nanosized Ni(OH) powders, which were firstly prepared through the room temperature solid state reaction between NiSO_4·6H_2O and NaOH) by H_2 at 400℃for 4 h and a series of palladium and platinum catalysts supported on NiO were prepared. The samples were characterized using XRD、TEM、SEM、IR、XPS and BET methods. The catalytic activity of the obtained nanosized Ni powders for hydrogenation of nitrobenzene, cinnamic aldehyde and maleic anhydride was investigated. The catalysts we made had high stability in the air and maintained the configuration of catalysts during the reaction process.The experimental results shown that the catalysts we made had high stability in the air and maintained the configuration of catalysts during the reaction process. Supporting palladium and platinum hadn’t changed the configuration of the sample. It suggested that the obtained nanosized Ni powders behaved better catalytic activity for hydrogenation of nitrobenzene to aniline than Raney-Ni. The experimental results shown that the catalyst improved by metal Pd had higher activity than the catalyst improved by metal Pt in hydrogenation of cinnamic aldehyde and the nanosized Ni powders shown high catalytic activity for hydrogenation of maleic anhydride.
2. The studies of the catalytic activity for nitrobenzene hydrogenation
The catalytic activity of as-prepared Ni powders for hydrogenation of nitrobenzene to aniline was studied, and the factors such as temperature, catalyst amount and H2
固相法制备纳米Ni粉:以NiSO_4·6H_2O和NaOH为原料,首先采用室温固相法制备纳米Ni(OH)_2粉,经过95%乙醇和蒸馏水交替洗涤去除其中的Na+、SO42-等杂质离子,得到草绿色粉末;粉末再经过110℃烘干8h,350℃焙烧4h、得到黑色粉末纳米NiO;NiO在加热炉中通入氢气还原,400℃还原4h得到灰黑色纳米Ni粉。以NiO为载体采用浸渍法分别掺杂不同含量的Pd、Pt等贵金属对此催化剂进行改性,制得Pd/Ni、Pt/Ni催化剂。采用XRD、TEM、SEM、IR、XPS、BET等手段对催化剂进行了表征。结果表明制备的纳米Ni粉为结构稳定、纯度高、粒径分布均匀的纳米颗粒,平均粒径在20-25nm;掺杂贵金属Pd、Pt后,产物的结构没有发生明显的变化,只是粒径有所增大。所制得的催化剂在空气中均能稳定存放,不易失活,并且在催化剂使用过程中仍保持结构完整。以硝基苯、肉桂醛、马来酸酐等物质的加氢反应为探针实验考察了催化剂的活性。实验发现,纳米Ni粉在硝基苯催化加氢反应中表现出很好的活性,在相同的条件下与Raney-Ni相比,纳米Ni粉具有更好的加氢效果,在工业生产中具有广阔的应用前景。在肉桂醛催化加氢反应中,贵金属Pd对催化剂的改性效果远比贵金属Pt优越。马来酸酐的转化率和选择性都很高,丁二酸酐的收率高达98.7%
二、硝基苯催化加氢性能研究
以硝基苯加氢制备苯胺为探针反应,考察了纳米Ni粉及掺杂贵金属Pd、Pt催化剂的加氢性能,并在相同条件下与Raney-Ni做了比较;同时考察了反应温度、催化剂用量、氢气压力等因素对催化剂反应活性的影响。结果发现,120℃、催化剂用量在～4%,对硝基苯加氢反应有利;同时还发现氢气压力对硝基苯转化率有明显的影响,在催化剂用量为2.0%,120℃反应10h,氢气压力为0.8MPa条件下,硝基苯转化率高达76.42%,苯胺的选择性为100%;在相同的条件下,纳米Ni粉作为催化剂,硝基苯加氢的转化率选择性和选择性比Raney-Ni优越的多,硝基
1. Preparation and characterization of catalysts
Nickel (NiO) powders with the sizes in the range of 20–25 nm were prepared via the reduction of nanosized NiO powders (The nanosized NiO powders were derived from low temperature (350℃) calcinations in air of nanosized Ni(OH) powders, which were firstly prepared through the room temperature solid state reaction between NiSO_4·6H_2O and NaOH) by H_2 at 400℃for 4 h and a series of palladium and platinum catalysts supported on NiO were prepared. The samples were characterized using XRD、TEM、SEM、IR、XPS and BET methods. The catalytic activity of the obtained nanosized Ni powders for hydrogenation of nitrobenzene, cinnamic aldehyde and maleic anhydride was investigated. The catalysts we made had high stability in the air and maintained the configuration of catalysts during the reaction process.The experimental results shown that the catalysts we made had high stability in the air and maintained the configuration of catalysts during the reaction process. Supporting palladium and platinum hadn’t changed the configuration of the sample. It suggested that the obtained nanosized Ni powders behaved better catalytic activity for hydrogenation of nitrobenzene to aniline than Raney-Ni. The experimental results shown that the catalyst improved by metal Pd had higher activity than the catalyst improved by metal Pt in hydrogenation of cinnamic aldehyde and the nanosized Ni powders shown high catalytic activity for hydrogenation of maleic anhydride.
2. The studies of the catalytic activity for nitrobenzene hydrogenation
The catalytic activity of as-prepared Ni powders for hydrogenation of nitrobenzene to aniline was studied, and the factors such as temperature, catalyst amount and H2
引文
(1)秦斌,盛光敏,黄家伟. 纳米镍粉在钛合金-不锈钢扩散焊接中的应用. 核动力工程,5(2004):457-432
(2)周波,盛光敏,黄家伟. 钛合金与不锈钢的纳米扩散焊接工艺探索. 焊接技术,1(2004):15-18
(3)何焕华. 世界镍工业现状及发展趋势. 有色冶炼,6(2001):1-3
(4)李瑞兴. 有色金属进展. 第四卷,有色金属,长沙:中国工业大学出版社,1995
(5)江治,李疏芬,李凯. 含纳米金属粉的推进剂点火实验及燃烧性能研究. 固体火箭技术,27(2004):117-120
(6)王军,宋永才,冯春祥. 聚碳硅烷/纳米镍粉的热裂解. 应用化学,2(1997):90-92
(7)Braos G P, Mairelles T P, Rodriguez C E. Gas-phase hydrogenation of acetonitrile on zirconium-doped mesoporous silica-supported nickel catalysts.[J]. Journal of Molecular Catalysis A :Chemical ,193(2003) :185–196
(8)Jinzhang Gao, Fei Guan, Yanchun Zhao. Preparation of ultrafine nickel powder and its catalytic dehydrogenation activity.[J]. Materials Chemistry and Physics 71 (2001):215–219
(9)Michio NODA, Sumio SHINODA, Yasukazu SARR. Liquid-phase dehydrogenation of 2-propanol by suspended nickel fine-particle catalyst . Bull.Chem.Soc.Jpn, 3(1988).
(10)江治,李疏芬. 纳米金属粉的制备及特性. 固体火箭技术, 24(2001):41-45.
(11)左东华,张志琨,催作林等. 纳米镍在硝基苯加氢中催化性能的研究. 分子催化. 9(1995):298-302.
(12)谈玲华,李勤华,杨毅. 纳米镍粉的制备及其催化性能研究. 固体火箭技术, 27(2004):198-200
(13)Kening Yu, Dong J. Kim, Hun S. Chung. Dispersed rodlike nickel powder synthesized by modified polyol process.[J].Materials Letters 57 (2003) :3992–3997
(14)Y.D. Li, C.W. Li, H.R. Wang. Preparation of nickel ultra powder and crystalline film by chemical control reduction.[J]. Materials Chemistry and Physics 59(1999) :88-90
(15)Wenjea J,Tseng, S.-Y. Lin. Effect of polymeric surfactant on flow behaviors of nickel–ethanol–isopropanol suspensions.[J]. Materials Science and Engineering A:362 (2003) 160–166
(16)Andrej Degen, JaDran Macek. Preparation of submicrometer nickel powders by the reduction from nanoqueous media.[J]. Nanosructured Materials 12 (1999):225-228
(17)C. Wang, X.M. Zhang, X.F. Qian. Preparation of namocrystalline nickel powders through hydrothmal-reduction method.[J]. Materials Research Bulletin, 33(1998):1747–1751,
(18)I.T.H. Chang, Z. Ren.Simple processing method and characterization of nanosized metal powders. [J]. Materials Science and Engineering A 375–377 (2004) 66–71
(19)谈玲华,李凤生,刘磊力. 纳米镍粉的制备的研究进展. 材料学报, 17 (2003):41-43
(20)牛明勤,吴介达. 超细镍粉的制备进展. 精细化工, 20(2003):715-717
(21)R.Brirringer, H.Gleiter, H.P.Klein. Nanocrystalline materials an approach to a novel solid structure with gas-like disorder. [J]. Phys.Lett. A 102(1984):365-369
(22)孙维民,金寿日,李志杰. 提高 Ni、Cu 超微粉生产率的方法研究. 应用科学学报,18(2000):164
(23)美国金属学会主编 金属手册(中文版),第九版,第七卷,粉末冶金[M] 韩凤麟主译 北京:机械工业出版社,1994:189-194
(24)屈子梅. 羰基法生产纳米镍粉. 粉末冶金工业,13(2003):16-20
(25)刘艳真,张景林,黄浩. 氧化还原法制备纳米镍粉研究. 应用化工, 34(2005):240-242
(26)李鹏,官建国,张清杰等. 1 ,2 丙二醇液相还原法制备纳米镍粉的研究. 材料科学与工艺, 9(2001):260-262.
(27)Hua-gui Zheng, Jia-he Liang, Jing-hui Zeng. Preparation of nickel nanopowders inethanol-water system (EWS) .[J]. Materials Research Bulletin 36 (2001) :947–952
(28)吴阳红. 微细镍粉的研制. 有色矿冶 16(2000):45-48
(29)张楠,翟秀静,翟玉春. 超细镍粉的溶液还原法制备研究. 功能材料,30(1999):263-267
(30)Kwang Ho Kim, Yoon Bok Lee , Eun Young Choi. Synthesis of nickel powders from various aqueous media through chemical reduction method.[J]. Materials Chemistry and Physics 86 (2004) :420–424
(31)S. Kapoor, H.G. Salunke, A.K. Tripathi. Radiolytic preparation and catalytic properties of nanophase nickel metal particles.[J]. Materials Research Bulletin 35 (2000) :143–148
(32)Yuanzhu Mi, Dingsheng Yuan, Yingliang Liu.Synthesis of hexagonal close-packed nanocrystalline nickel by a thermal reduction process.[J]. Materials Chemistry and Physics 89 (2005): 359–361
(33)M. Arturo, López-Quintela, José Rivas. Chemical Reactions in Microemulsions: A Powerful Method to Obtain Ultrafine Particles. [J]. J Colloid Interface Sci,1993, 158: 446-451
(34)徐菊,喻克宁,梁换诊等. 用Ni(OH)2浆化氢还原法制备纳米金属镍粉的反应机制. 材料研究学报, 16(2002):158-163
(35)喻克宁,胡嗣强,毛铭华等. Ni(OH)2水热氢还原制备超细Ni粉. 材料研究学报, 9(1995):223-227
(36)Mcfadden S X, Mishra R S, Valiev R Z, et al. Low-temperature superplasticity in nanostructured nickel and metal alloys.[J].lett.to nature,1999,398:684
(37)何峰,张正义,肖耀福等. 制备超细金属粉末的新型电解法. 金属学报, 36(2000):659-661
(38)施云波,陈耐生. 纳米技术在半导体陶瓷气体传感器中的应用. 6(2000)1-6
(39)Baburaj E G, Hubert K T, Fores F H S. Preparation of Ni powder by mechanochemical process.[J]. J Alloy Compd , 257(1997):146 -149.
(40)Wei-Ning Wang, Yoshifumi Itoh, I. Wuled Lenggoro, Kikuo Okuyama. Nickel and nickel oxide nanoparticles prepared from nickel nitrate hexahydrate by a low pressure spray pyrolysis.[J]. Materials Science and Engineering B 111 (2004) 69–76
(41)Yun Chang Kang, Seung Bin Park, Yun Whan Kang. Preparation of high surface area nanophase particles by pressure spray pyrolysis.[J]. Nanostructure Materials 5(1995):777-791
(42)陶刚,催克清. 硝基苯催化加氢制苯胺的技术分析. 氯碱工业, 7(2001):24-17
(43)皮现玉. 苯胺的合成方法与应用. 氯碱工业, 6(1999):34-35
(44)汪智国,景山,魏飞. 硝基苯在湍动流化床加氢制取苯胺. 化学反应工程与工艺, 17(2001):278-281
(45)金栋,崔小明. 国内外苯胺的生产应用及市场分析. 化工中间体,15(2002):3-6
(46)方向明. 硝基苯气相加氢催化剂 CuO/SiO2 的改性研究. 应用化学,14(1997):57-59 [47] 崔 小 明 . 国 内 外 苯 胺 的 生 产 应 用 及 市 场 分 析 . 石 油 化 工 技 术 经济,18(2002):32-38
(48)催小明. 苯胺的生产应用及市场分析(下). 上海化工,21(2002):35-38
(49)宋啸平,黄美玉,江英彦. 羊毛负载钯络合物的合成及其加氢催化作用. 分子催化,1(1994):8-13
(50)B. Amon, H. Redlingsho fer, E. Klemm. Kinetic investigations of the deactivation by coking of a noble metal catalyst in the catalytic hydrogenation of nitrobenzene using a catalytic wall reactor .[J]. Chemical Engineering and Processing 38 (1999) :395–404
(51)Shao-Pai Lee, Yu-Wen Chen. Nitrobenzene hydrogenation on Ni–P, Ni–B and Ni–P–B ultrafine materials .[J]. Journal of Molecular Catalysis A: Chemical 152(2000):213–223
(52)郭延红,郭力民,孙小燕. 硝基苯加氢制备苯胺的催化体系研究进展. 化学工程师, 2(2004):24-25
(53)杨庆荣. 苯胺的生产现状及市场分析. 河南化工,22(2005):12-52
(54)Jacek Kijensk i, Piotr Winiarek. Selective hydrogenation of α,β-unsaturated aldehydes over Pt catalysts deposited on monolayer supports.[J ]. Applied Cataylsis A: General, 193(2000):L1-L4
(55)Delbecq F, Sautet P. Competitive C=C and C=O adsorption of αβ-unsaturated aldehydes on P t and Pd surface in relation with the selectivity of hydrogenation reactions: a theoretical approach. [J ]. J Catal, 152(1995): 217.
(56)陈兴凡,徐叶平,蔡霞等. Co-B 非晶态合金催化肉桂醛液相选择性加氢制备肉桂醇的研究. 化学研究及应用,14(2002):269-273
(57)沙广燕,肖进兵,扬光等. 氧化钼上肉桂醛的选择加氢. 大连大学学报, 24(2003):59-62
(58)刘百军,熊国兴,潘秀莲等. 贵金属对钴基催化剂上肉桂醛选择加氢反应的影响. 催化学报,23(2002):481-484
(59)牛文兴. 丁二酸酐的生产及应用. 辽宁化工,6(1994): 30-31
(60)盛兴,芮斌. 马来酸酐的接枝应用. 湖北化工,2003增刊:25-26
(61)肖新荣,李珊,赵成祥. 固体酸催化合成富马酸二甲酯. 南华大学学报(理工版),18(2004):76-78
(62)沈常美. 2005 年扬州大学硕士学位毕业论文.2005:17
(63)Xiaohong Liu, Lan Yu. Synthesis of nanosized nickel hydroxide by solid-state reaction at room temperature.[J]. Materials Letters 58(2004):1327-1330
(64)李生英,高锦章,杨武. 固相合成纳米NiO微粒. 西北师范大学学报,39(2003):46-48
(65)汪国忠,张立德,牟季美. 纳米氧化镍微粉德制备及光吸收谱. 物理化学学报,13(1997):445-448
(66)Wu Lili, Wu Youshi Wei, Huiying. Synthesis and characteristics of NiO nanowire by a solution method . [J] . Materials Letters 58(2004):2700～2703.
(67)陈存敬,郭志猛,高峰. 纳米镍粉的粒度分析. 粉末冶金技术,22(2004):71-75
(68)秦振平,郭红霞,李东升. 缩聚多元醇液相还原法制备纳米镍粉及其表征. 功能材料与器件学报, 10(2004):95-97
(69)徐林. 2004年扬州大学硕士学位毕业论文.2004,21-22
(70)张在喜. 硝基苯加氢还原制苯胺生产技术的改进. 中国氯碱, 9(1999):33-35
(71)郭延红,郭力民,孙小燕. 硝基苯加氢制备苯胺的催化体系研究进展. 化学工程师,2(2004):24-25
(72)Bachiller-BaezaB, rodr?guez-RamosI, Guerrero-RuizA. Influence of Mg and Ce addition to ruthenium based catalysts used in the selective hydrogenation of α,β-unsaturated aldehydes. [J].Appl Catal, A, 205(2002): 227~233
(73)Wanida Koo-amornpattana., John Mike Winterbottom. Pt and Pt-alloy catalysts and their properties for the liquid-phase hydrogenation of cinnamaldehyde.[J]. Catalysis Today 66 (2001) 277–287
(74)PoltarzeweskiZ, GalvagnoS, PietropaonoR, et.al. Hydrogenation of α,β-unsaturated aldehydes over Pt-Sn/Nylon. [J]. J Catal, 1986, 102:190~198.
(75)Coq B, Khumbar P S, Moreau C, et.al. Liquid phase hydrogenation of cinnamaldehyde over supported ruthenium catalysts: influence of particle size, bimetallics andnature of support.[J].J Mol Catal,1993,85:215~218.
(76)周仁贤,韩小祥,赖国华等. 负载铂催化剂上 α,β-不饱和醛选择性加氢性能的研究. 第十二届全国催化学术会议论文集:398-400
(77)Liu Pu, Liu Ye, Yin Yuanqi. Homogeneous hydrogenation of maleic anhydride to succinic anhydride catalyzed by Rh complex catalyst.[J]. Journal of Molecular Catalysis A: Chemical 138 1999 129–133
(78)试剂手册. 上海科学技术出版社.1984年,第二版:1159
(2)周波,盛光敏,黄家伟. 钛合金与不锈钢的纳米扩散焊接工艺探索. 焊接技术,1(2004):15-18
(3)何焕华. 世界镍工业现状及发展趋势. 有色冶炼,6(2001):1-3
(4)李瑞兴. 有色金属进展. 第四卷,有色金属,长沙:中国工业大学出版社,1995
(5)江治,李疏芬,李凯. 含纳米金属粉的推进剂点火实验及燃烧性能研究. 固体火箭技术,27(2004):117-120
(6)王军,宋永才,冯春祥. 聚碳硅烷/纳米镍粉的热裂解. 应用化学,2(1997):90-92
(7)Braos G P, Mairelles T P, Rodriguez C E. Gas-phase hydrogenation of acetonitrile on zirconium-doped mesoporous silica-supported nickel catalysts.[J]. Journal of Molecular Catalysis A :Chemical ,193(2003) :185–196
(8)Jinzhang Gao, Fei Guan, Yanchun Zhao. Preparation of ultrafine nickel powder and its catalytic dehydrogenation activity.[J]. Materials Chemistry and Physics 71 (2001):215–219
(9)Michio NODA, Sumio SHINODA, Yasukazu SARR. Liquid-phase dehydrogenation of 2-propanol by suspended nickel fine-particle catalyst . Bull.Chem.Soc.Jpn, 3(1988).
(10)江治,李疏芬. 纳米金属粉的制备及特性. 固体火箭技术, 24(2001):41-45.
(11)左东华,张志琨,催作林等. 纳米镍在硝基苯加氢中催化性能的研究. 分子催化. 9(1995):298-302.
(12)谈玲华,李勤华,杨毅. 纳米镍粉的制备及其催化性能研究. 固体火箭技术, 27(2004):198-200
(13)Kening Yu, Dong J. Kim, Hun S. Chung. Dispersed rodlike nickel powder synthesized by modified polyol process.[J].Materials Letters 57 (2003) :3992–3997
(14)Y.D. Li, C.W. Li, H.R. Wang. Preparation of nickel ultra powder and crystalline film by chemical control reduction.[J]. Materials Chemistry and Physics 59(1999) :88-90
(15)Wenjea J,Tseng, S.-Y. Lin. Effect of polymeric surfactant on flow behaviors of nickel–ethanol–isopropanol suspensions.[J]. Materials Science and Engineering A:362 (2003) 160–166
(16)Andrej Degen, JaDran Macek. Preparation of submicrometer nickel powders by the reduction from nanoqueous media.[J]. Nanosructured Materials 12 (1999):225-228
(17)C. Wang, X.M. Zhang, X.F. Qian. Preparation of namocrystalline nickel powders through hydrothmal-reduction method.[J]. Materials Research Bulletin, 33(1998):1747–1751,
(18)I.T.H. Chang, Z. Ren.Simple processing method and characterization of nanosized metal powders. [J]. Materials Science and Engineering A 375–377 (2004) 66–71
(19)谈玲华,李凤生,刘磊力. 纳米镍粉的制备的研究进展. 材料学报, 17 (2003):41-43
(20)牛明勤,吴介达. 超细镍粉的制备进展. 精细化工, 20(2003):715-717
(21)R.Brirringer, H.Gleiter, H.P.Klein. Nanocrystalline materials an approach to a novel solid structure with gas-like disorder. [J]. Phys.Lett. A 102(1984):365-369
(22)孙维民,金寿日,李志杰. 提高 Ni、Cu 超微粉生产率的方法研究. 应用科学学报,18(2000):164
(23)美国金属学会主编 金属手册(中文版),第九版,第七卷,粉末冶金[M] 韩凤麟主译 北京:机械工业出版社,1994:189-194
(24)屈子梅. 羰基法生产纳米镍粉. 粉末冶金工业,13(2003):16-20
(25)刘艳真,张景林,黄浩. 氧化还原法制备纳米镍粉研究. 应用化工, 34(2005):240-242
(26)李鹏,官建国,张清杰等. 1 ,2 丙二醇液相还原法制备纳米镍粉的研究. 材料科学与工艺, 9(2001):260-262.
(27)Hua-gui Zheng, Jia-he Liang, Jing-hui Zeng. Preparation of nickel nanopowders inethanol-water system (EWS) .[J]. Materials Research Bulletin 36 (2001) :947–952
(28)吴阳红. 微细镍粉的研制. 有色矿冶 16(2000):45-48
(29)张楠,翟秀静,翟玉春. 超细镍粉的溶液还原法制备研究. 功能材料,30(1999):263-267
(30)Kwang Ho Kim, Yoon Bok Lee , Eun Young Choi. Synthesis of nickel powders from various aqueous media through chemical reduction method.[J]. Materials Chemistry and Physics 86 (2004) :420–424
(31)S. Kapoor, H.G. Salunke, A.K. Tripathi. Radiolytic preparation and catalytic properties of nanophase nickel metal particles.[J]. Materials Research Bulletin 35 (2000) :143–148
(32)Yuanzhu Mi, Dingsheng Yuan, Yingliang Liu.Synthesis of hexagonal close-packed nanocrystalline nickel by a thermal reduction process.[J]. Materials Chemistry and Physics 89 (2005): 359–361
(33)M. Arturo, López-Quintela, José Rivas. Chemical Reactions in Microemulsions: A Powerful Method to Obtain Ultrafine Particles. [J]. J Colloid Interface Sci,1993, 158: 446-451
(34)徐菊,喻克宁,梁换诊等. 用Ni(OH)2浆化氢还原法制备纳米金属镍粉的反应机制. 材料研究学报, 16(2002):158-163
(35)喻克宁,胡嗣强,毛铭华等. Ni(OH)2水热氢还原制备超细Ni粉. 材料研究学报, 9(1995):223-227
(36)Mcfadden S X, Mishra R S, Valiev R Z, et al. Low-temperature superplasticity in nanostructured nickel and metal alloys.[J].lett.to nature,1999,398:684
(37)何峰,张正义,肖耀福等. 制备超细金属粉末的新型电解法. 金属学报, 36(2000):659-661
(38)施云波,陈耐生. 纳米技术在半导体陶瓷气体传感器中的应用. 6(2000)1-6
(39)Baburaj E G, Hubert K T, Fores F H S. Preparation of Ni powder by mechanochemical process.[J]. J Alloy Compd , 257(1997):146 -149.
(40)Wei-Ning Wang, Yoshifumi Itoh, I. Wuled Lenggoro, Kikuo Okuyama. Nickel and nickel oxide nanoparticles prepared from nickel nitrate hexahydrate by a low pressure spray pyrolysis.[J]. Materials Science and Engineering B 111 (2004) 69–76
(41)Yun Chang Kang, Seung Bin Park, Yun Whan Kang. Preparation of high surface area nanophase particles by pressure spray pyrolysis.[J]. Nanostructure Materials 5(1995):777-791
(42)陶刚,催克清. 硝基苯催化加氢制苯胺的技术分析. 氯碱工业, 7(2001):24-17
(43)皮现玉. 苯胺的合成方法与应用. 氯碱工业, 6(1999):34-35
(44)汪智国,景山,魏飞. 硝基苯在湍动流化床加氢制取苯胺. 化学反应工程与工艺, 17(2001):278-281
(45)金栋,崔小明. 国内外苯胺的生产应用及市场分析. 化工中间体,15(2002):3-6
(46)方向明. 硝基苯气相加氢催化剂 CuO/SiO2 的改性研究. 应用化学,14(1997):57-59 [47] 崔 小 明 . 国 内 外 苯 胺 的 生 产 应 用 及 市 场 分 析 . 石 油 化 工 技 术 经济,18(2002):32-38
(48)催小明. 苯胺的生产应用及市场分析(下). 上海化工,21(2002):35-38
(49)宋啸平,黄美玉,江英彦. 羊毛负载钯络合物的合成及其加氢催化作用. 分子催化,1(1994):8-13
(50)B. Amon, H. Redlingsho fer, E. Klemm. Kinetic investigations of the deactivation by coking of a noble metal catalyst in the catalytic hydrogenation of nitrobenzene using a catalytic wall reactor .[J]. Chemical Engineering and Processing 38 (1999) :395–404
(51)Shao-Pai Lee, Yu-Wen Chen. Nitrobenzene hydrogenation on Ni–P, Ni–B and Ni–P–B ultrafine materials .[J]. Journal of Molecular Catalysis A: Chemical 152(2000):213–223
(52)郭延红,郭力民,孙小燕. 硝基苯加氢制备苯胺的催化体系研究进展. 化学工程师, 2(2004):24-25
(53)杨庆荣. 苯胺的生产现状及市场分析. 河南化工,22(2005):12-52
(54)Jacek Kijensk i, Piotr Winiarek. Selective hydrogenation of α,β-unsaturated aldehydes over Pt catalysts deposited on monolayer supports.[J ]. Applied Cataylsis A: General, 193(2000):L1-L4
(55)Delbecq F, Sautet P. Competitive C=C and C=O adsorption of αβ-unsaturated aldehydes on P t and Pd surface in relation with the selectivity of hydrogenation reactions: a theoretical approach. [J ]. J Catal, 152(1995): 217.
(56)陈兴凡,徐叶平,蔡霞等. Co-B 非晶态合金催化肉桂醛液相选择性加氢制备肉桂醇的研究. 化学研究及应用,14(2002):269-273
(57)沙广燕,肖进兵,扬光等. 氧化钼上肉桂醛的选择加氢. 大连大学学报, 24(2003):59-62
(58)刘百军,熊国兴,潘秀莲等. 贵金属对钴基催化剂上肉桂醛选择加氢反应的影响. 催化学报,23(2002):481-484
(59)牛文兴. 丁二酸酐的生产及应用. 辽宁化工,6(1994): 30-31
(60)盛兴,芮斌. 马来酸酐的接枝应用. 湖北化工,2003增刊:25-26
(61)肖新荣,李珊,赵成祥. 固体酸催化合成富马酸二甲酯. 南华大学学报(理工版),18(2004):76-78
(62)沈常美. 2005 年扬州大学硕士学位毕业论文.2005:17
(63)Xiaohong Liu, Lan Yu. Synthesis of nanosized nickel hydroxide by solid-state reaction at room temperature.[J]. Materials Letters 58(2004):1327-1330
(64)李生英,高锦章,杨武. 固相合成纳米NiO微粒. 西北师范大学学报,39(2003):46-48
(65)汪国忠,张立德,牟季美. 纳米氧化镍微粉德制备及光吸收谱. 物理化学学报,13(1997):445-448
(66)Wu Lili, Wu Youshi Wei, Huiying. Synthesis and characteristics of NiO nanowire by a solution method . [J] . Materials Letters 58(2004):2700～2703.
(67)陈存敬,郭志猛,高峰. 纳米镍粉的粒度分析. 粉末冶金技术,22(2004):71-75
(68)秦振平,郭红霞,李东升. 缩聚多元醇液相还原法制备纳米镍粉及其表征. 功能材料与器件学报, 10(2004):95-97
(69)徐林. 2004年扬州大学硕士学位毕业论文.2004,21-22
(70)张在喜. 硝基苯加氢还原制苯胺生产技术的改进. 中国氯碱, 9(1999):33-35
(71)郭延红,郭力民,孙小燕. 硝基苯加氢制备苯胺的催化体系研究进展. 化学工程师,2(2004):24-25
(72)Bachiller-BaezaB, rodr?guez-RamosI, Guerrero-RuizA. Influence of Mg and Ce addition to ruthenium based catalysts used in the selective hydrogenation of α,β-unsaturated aldehydes. [J].Appl Catal, A, 205(2002): 227~233
(73)Wanida Koo-amornpattana., John Mike Winterbottom. Pt and Pt-alloy catalysts and their properties for the liquid-phase hydrogenation of cinnamaldehyde.[J]. Catalysis Today 66 (2001) 277–287
(74)PoltarzeweskiZ, GalvagnoS, PietropaonoR, et.al. Hydrogenation of α,β-unsaturated aldehydes over Pt-Sn/Nylon. [J]. J Catal, 1986, 102:190~198.
(75)Coq B, Khumbar P S, Moreau C, et.al. Liquid phase hydrogenation of cinnamaldehyde over supported ruthenium catalysts: influence of particle size, bimetallics andnature of support.[J].J Mol Catal,1993,85:215~218.
(76)周仁贤,韩小祥,赖国华等. 负载铂催化剂上 α,β-不饱和醛选择性加氢性能的研究. 第十二届全国催化学术会议论文集:398-400
(77)Liu Pu, Liu Ye, Yin Yuanqi. Homogeneous hydrogenation of maleic anhydride to succinic anhydride catalyzed by Rh complex catalyst.[J]. Journal of Molecular Catalysis A: Chemical 138 1999 129–133
(78)试剂手册. 上海科学技术出版社.1984年,第二版:1159