PdAu/Al2O3合金纳米催化剂的合成、表征及其在4-氯硝基苯加氢中的应用
PDF下载 (437)谢朝辉 1,于洪波 2,刘进军 1*.PdAu/Al2O3合金纳米催化剂的合成、表征及其在4-氯硝基苯加氢中的应用[J].宁波大学学报(理工版),2016,29(4):72-76.DOI:
XIE Zhao-hui 1,YU Hong-bo 2,LIU Jin-jun 1*.Synthesis, Characterization and Catalytic Activity of PdAu/Al2O3 for p-Chloronitrobenzene Hydrogenation[J].Journal of Ningbo University(Natural Science & Engineering Edition),2016,29(4):72-76.DOI:
| Title: | Synthesis, Characterization and Catalytic Activity of PdAu/Al2O3 for p-Chloronitrobenzene Hydrogenation |
| 作者: | 谢朝辉 1, 于洪波 2, 刘进军 1* |
| Author(s): | XIE Zhao-hui 1, YU Hong-bo 2, LIU Jin-jun 1* |
| 关键词: | PdAu合金纳米颗粒; 尺寸可控; 催化加氢; 4-氯硝基苯 |
| Keywords: | PdAu nano-alloy particle; size controlled; catalytic hydrogenation; p-chloronitrobenzene |
| 分类号: | O643.3 |
| 文献标识码: | A |
| 摘要: | 采用乙二醇连续还原法合成了不同摩尔比的PdAu合金纳米颗粒. 利用XRD、TEM、DRIFT-IR和紫外可见光光谱表征技术对其进行了表征. 结果表明, 纳米Pd种子与氯金酸钠发生置换反应, 表面元素重新排布, Pd、Au纳米颗粒以PdAu合金形式存在, 且合金粒径大小可控. 将不同摩尔比的PdAu合金纳米颗粒采用共沉淀法负载到Al2O3载体上, 制得PdAu/Al2O3催化剂, 并将其应用于4-氯硝基苯的加氢反应中. 与Au/Al2O3、Pd/Al2O3催化剂(4-氯硝基苯转化率为0和37.4%)相比, PdAu/Al2O3催化剂大大提高了4-氯硝基苯加氢活性, 其中PdAu-1/0.5/Al2O3催化剂具有最高的催化活性, 4-氯硝基苯转化率为69.4%, 这可能归因于PdAu合金纳米颗粒间的协同效应和PdAu与Al2O3载体间的强相互作用. |
| Abstract: | PdAu alloy nanoparticles with different molar ratio have been synthesized via sequential reduction method using glycol as the reductant. The results of XRD, TEM, DRIFT-IR and UV-visible spectra indicate that Au in sodium tetrachloroaurate (NaAuCl4) is partially replaced by Pd, resulting with the rearrangement of the surface atoms, thus the nanoparticles of Pd and Au are generated in the form of PdAu alloy with controllable particle size. PdAu/Al2O3 catalyst is prepared using the co-precipitation method and applied for p- chloronitrobenzene (p-CNB) hydrogenation with H2. Compared with Au/Al2O3 (the conversion of p-CNB being 0) and Pd/Al2O3 (the conversion of p-CNB being 37.4%) catalysts, the catalytic performance of PdAu/Al2O3 catalyst is significantly improved, where PdAu-1/0.5/Al2O3 exhibits the best catalytic performance with the highest conversion of p-CNB being 69.4%, which is probably attributed to the synergistic effect among PdAu nanoparticles and strong interaction between PdAu and Al2O3 support. |
| 参考文献 /References: | [1] 周颖, 陈立宇, 李映伟. 纳米多相催化材料在常温反应中的应用[J]. 化工进展, 2015, 34(10):3530-3539. [2] SU R, TIRUVALAM R, HE Q, et al. Promotion of phenol photodecomposition over TiO2 using Au, Pd, and Au- Pd nanoparticles[J]. ACS Nano, 2012, 6(7):6284-6292. [3] XU J, WHITE T, LI P, et al. Biphasic Pd-Au alloy catalyst for low-temperature CO oxidation[J]. J Am Chem Soc, 2010, 132(30):10398-10406. [4] HECK K N, NUTT M O, ALVAREZ P, et al. Deactivation resistance of Pd/Au nanoparticle catalysts for water-phase hydrodechlorination[J]. J Catal, 2009, 267(2):97-104. [5] DIMITRATOS N, LOPEZ-SANCHEZ J A, MEENAKSHISUNDARAM S, et al. Selective formation of lactate by oxidation of 1,2-propanediol using gold palladium alloy supported nanoparticles[J]. Green Chem, 2009, 11(8):1209-1216. [6] OKAMOTO H, MASSALSKI T B. Alloy phase diagrams [EB/OL]. [2015-12-10]. http://products. asminternational. org/hbk/index.jsp. [7] LIM B, KOBAYASHI H, YU T, et al. Synthesis of Pd-Au bimetallic nanocrystals via controlled overgrowth [J]. J Am Chem Soc, 2010, 132(8):2506-2507. [8] ZHANG K, XIANG Y J, WU X C, et al. Enhanced optical responses of Au@Pd core/shell nanobars[J]. Langmuir, 2009, 25(2):1162-1168. [9] ZHU C, ZENG J, TAO J, et al. Kinetically controlled overgrowth of Ag or Au on Pd nanocrystal seeds: From hybrid dimers to nonconcentric and concentric bimetallic nano crystals[J]. J Am Chem Soc, 2012, 134(38):15822-15831. [10] DING Y, FAN F R, TIAN Z Q, et al. Atomic structure of Au-Pd bimetallic alloyed nanoparticles[J]. J Am Chem Soc, 2010, 132(35):12480-12486. [11] ZHAI Y M, ZHAI J F, DONG S J. Temperature- dependent synthesis of CoPt hollow nanoparticles: From “Nanochain” to “Nanoring”[J]. Chem Commun, 2010, 46(9):1500-1502. [12] CHEN X B, NARAYANAN R, BURDA C, et al. Chemistry and properties of nanocrystals of different shapes[J]. Chem Rev, 2005, 105(4):1025-1102. [13] TAUSTER S J. Strong metal-support interactions[J]. Acc Chem Res, 1987, 20(11):389-394. [14] MOLINER M, SERNA P, CANTIN A, et al. Synthesis of the Ti-silicate form of BEC polymorph of beta-zeolite assisted by molecular modeling[J]. J Phys Chem C, 2008, 112(49):19547-19554. [15] LIU X Y, LIU M H, LUO Y C, et al. Strong metal-support interactions between gold nano-particles and ZnO nanorods in CO oxidation[J]. J Am Chem Soc, 2012, 134(24):10251-10258. [16] WANG X D, PERRET N, DELGADO J J, et al. Reducible support effects in the gas phase hydrogenation of p-chloronitrobenzene over gold[J]. J Phys Chem C, 2013, 117(2):994-1005. [17] SUN Y G, XIA Y N. Shape-controlled synthesis of gold and silver nanoparticles[J]. Science, 2002, 298(5601): 2176-2179. [18] XIONG Y J, CHEN J Y, WILEY B, et al. Understanding the role of oxidative etching in the polyol synthesis of Pd nanoparticles with uniform shape and size[J]. J Am Chem Soc, 2005, 127(20):7332-7333. [19] ZHANG P P, HU Y B, LI B H, et al. Kinetically stabilized Pd@Pt core-shell octahedral nanoparticles with thin Pt layers for enhanced catalytic hydrogenation performance[J]. ACS Catal, 2015, 5(2):1335-1343. [20] BULUSHEV D A, BELOSHAPKIN S, PLYUSNIN P E, et al. Vapour phase formic acid decomposition over PdAu/c-Al2O3 catalysts: Effect of composition of metallic particles[J]. J Catal, 2013, 299:171-180. [21] JOHNSON S R, RVANS S D, MAHON S W, et al. Alkanethiol molecules containing an aromatic moiety self-assembled onto gold clusters[J]. Langmuir, 1997, 13(1):51-57. |
| 备注/Memo: | 收稿日期: 2016－01－11. 宁波大学学报（理工版）网址: http://journallg.nbu.edu.cn/ 基金项目: 国家自然科学基金（11375091）; 宁波市自然科学基金（2011A610171）; 宁波大学学科项目（xkzwl03）. 第一作者: 谢朝辉（1989－）, 男, 湖南永州人, 在读硕士研究生, 主要研究方向: 纳米材料制备与多相催化. E-mail: xiezhaohui@nimte.ac.cn *通信作者: 刘进军（1980－）, 男, 山西阳泉人, 助理研究员, 主要研究方向: 非平衡统计与复杂系统. E-mail: liujinjun@nbu.edu.cn 宁波大学学报（理工版）网址：http://journallg.nbu.edu.cn/ |
