采用均匀沉积-沉淀法制备了氧化铜修饰羟基磷灰石负载金催化剂(Au/CuO-HAP),并用原子吸收光谱、N2吸附脱附、X射线粉末衍射、透射电镜和X射线光电子能谱等方法对催化剂结构和形貌进行了表征.考察了催化剂对醇类液相需氧氧化的催化性能.与单金属Au/HAP或CuO-HAP相比较,双金属Au/CuO-HAP对苯甲醇氧化的催化活性和苯甲醛的选择性有显著提高,120 oC反应1.5 h,苯甲醇的转化率和苯甲醛的选择性分别达到99.7%和98.4%.在Au/CuO-HAP的催化下,其它类型的芳香醇均可高选择性转化为相应的醛或酮. Au/CuO-HAP催化剂有很好的稳定性和可回收性,4次回收后,其催化活性没有明显变化.
A catalyst consisting of Au supported on copper oxide-modified hydroxyapatite (Au/CuO-HAP) was prepared using a homogeneous deposition-precipitation method. The catalyst was characterized using atomic absorption spectrometry, N2 adsorption-desorption, powder X-ray diffraction, trans-mission electron microscopy, and X-ray photoelectron spectroscopy. The catalytic performance in liquid-phase aerobic oxidation of alcohols was investigated. The catalytic activity and benzaldehyde selectivity in benzyl alcohol oxidation with the bimetallic Au/CuO-HAP catalyst were significantly better than those with monometallic Au/HAP and CuO-HAP catalysts. The conversion of benzyl alcohol and selectivity for benzaldehyde at 120 °C for 1.5 h under aerobic oxidation conditions were 99.7%and 98.4%, respectively. Various aromatic alcohols were selectively converted to their cor-responding aldehydes or ketones over Au/CuO-HAP. The Au/CuO-HAP catalyst could be reused at least four times without loss of activity.
参考文献
| [1] | Sheldon R A;Kochi J K.Metal-Catalyzed Oxidations of Organic Compounds[M].New York:Academic Press,1981 |
| [2] | Cossio F P;Lopez M C;Palomo C .[J].Tetrahedron,1987,43:3963. |
| [3] | Lee D G;Spitzer U A .[J].J Org Chem,1970,35:3589. |
| [4] | Menger F M;Lee C .[J].J Org Chem,1979,44:3446. |
| [5] | Jefford C W;Wang Y.[M].J Chem Soc,Chem Commun,1988:634. |
| [6] | Weerasiri K C;Gorden A E V .[J].Tetrahedron,2014,70:7962. |
| [7] | Sato K;Aoki M;Takagi J;Noyori R .[J].J Am Chem Soc,1997,119:12386. |
| [8] | Dhakshinamoorthy A;Alvaro M;Garcia H .[J].ACS Catal,2011,1:48. |
| [9] | Dun R R;Wang X G;Tan M W;Huang Z,Huang X M,Ding W Z,Lu X G .[J].ACS Catal,2013,3:3063. |
| [10] | 王亮,孟祥举,肖丰收.水滑石负载Au纳米粒子的制备及其催化醇氧化反应[J].催化学报,2010(08):943-947. |
| [11] | Hong Y J;Yan X Q;Liao X F;Li R H,Xu S D,Xiao L P,Fan J .[J].Chem Commun,2014,50:9679. |
| [12] | Gopiraman M;Ganesh Babu S;Khatri Z;Kai W,Kim Y A,Endo M,Karvembu R,Kim I S .[J].J Phys Chem C,2013,117:23582. |
| [13] | Haruta M;Yamada N;Kobayashi T;lijima S .[J].J Catal,1989,115:301. |
| [14] | Haruta M;Tsubota S;Kobayashi T;Kageyama H,Genet M J,Delmon B .[J].J Catal,1993,144:175. |
| [15] | Wang Z;Xu C L;Wang H F .[J].Catal Lett,2014,144:1919. |
| [16] | Wang, L.;Zhang, W.;Sheng Su, D.;Meng, X.;Xiao, F.-S. .Supported Au nanoparticles as efficient catalysts for aerobic homocoupling of phenylboronic acid[J].Chemical communications,2012(44):5476-5478. |
| [17] | Kesavan L;Tiruvalam R;Ab Rahim M H;bin Saiman M I,Enache D I,Jenkins R L,Dimitratos N,Lopez-Sanchez J A,Taylor S H,Knight D W,Kiely C J,Hutchings G J .[J].Science,2011,331:195. |
| [18] | Enache DI;Edwards JK;Landon P;Solsona-Espriu B;Carley AF;Herzing AA;Watanabe M;Kiely CJ;Knight DW;Hutchings GJ .Solvent-free oxidation of primary alcohols to aldehydes using Au-Pd/TiO2 catalysts[J].Science,2006(5759):362-365. |
| [19] | Yang, X.;Chen, D.;Liao, S.;Song, H.;Li, Y.;Fu, Z.;Su, Y..High-performance Pd-Au bimetallic catalyst with mesoporous silica nanoparticles as support and its catalysis of cinnamaldehyde hydrogenation[J].Journal of Catalysis,2012:36-43. |
| [20] | Lopez-Sanchez J A;Dimitratos N;Glanville N;Kesavan L,Ham-mond C,Edwards J K,Carley A F,Kiely C J,Hutchings G J .[J].Appl Catal A,2011,391:400. |
| [21] | Zhao J G;Cheng X G;Wang L;Ren R F,Zeng J J,Yang H H,Shen B X .[J].Catal Lett,2014,144:2191. |
| [22] | Zhang H Y;Dai B;Wang X G;Li W,Han Y,Gu J J,Zhang J L .[J].Green Chem,2013,15:829. |
| [23] | Potemkin D I;Semitut E Yu;Shubin Yu V;Plyusnin P E,Snytnikov P V,Makotchenko E V,Osadchii D Y,Svintsiskiy D A,Venyaminov S A,Korenev S V,Sobyanin V A .[J].Catal Today,2014,235:103. |
| [24] | Nea?u;Maciá-Agulló J A;Concepción P;Garcia H .[J].J Am Chem Soc,2014,136:15969. |
| [25] | Yuan X;Zheng J W;Zhang Q;Li S R,Yang Y H,Gong J L .[J].AIChE J,2014,60:3300. |
| [26] | Jia Q Q;Zhao D F;Tang B;Zhao N,Li H D,Sang Y H,Bao N,Zhang XM,Xu X H,Liu H .[J].J Mater Chem A,2014,2:16292. |
| [27] | Li W J;Wang A Q;Liu X Y;Zhang T .[J].Appl Catal A,2012,433-434:146. |
| [28] | Wang, H.;Fan, W.;He, Y.;Wang, J.;Kondo, J.N.;Tatsumi, T..Selective oxidation of alcohols to aldehydes/ketones over copper oxide-supported gold catalysts[J].Journal of Catalysis,2013:10-19. |
| [29] | Zanella R;Giorgio S;Shin C H;Henry C R,Louis C .[J].J Catal,2004,222:357. |
| [30] | Wen C;Cui Y Y;Chen X;Zong B N,Dai W L .[J].Appl Catal B,2015,162:483. |
| [31] | Moulder J F;Stickle W F;Sobol P E;Bomben K D.Handbook of X-ray Photoelectron Spectroscopy[M].Minnesota:Physical Electron-ics,1995 |
| [32] | Wang L C;He L;Liu Q;Liu Y M,Chen M,Cao Y,He H Y,Fan K N .[J].Appl Catal A,2008,344:150. |
| [33] | 李娴,郑嘉旻,杨新丽,戴维林,范康年.高活性Au/SnO2催化剂的制备及其在1,4-丁二醇氧化制γ-丁内酯反应中的催化应用[J].催化学报,2013(05):1013-1019. |
| [34] | Hallett-Tapley G L;Silvero M J;Bueno-Alejo C J;González-Béjar M,McTiernan C D,Grenier M,Netto-Ferreira J C,Scaiano J C .[J].J Phys Chem C,2013,117:12279. |
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