研究了多种载体负载Pd催化剂上苯甲醇无氧脱氢反应.结果发现,以兼具较强酸性和碱性的水滑石(HT)为载体时,Pd催化剂具有优异的苯甲醇转化活性和苯甲醛选择性,当Pd含量为0.32%～0.55%时催化性能最佳.Pd/HT催化剂可重复使用,且对于含推电子取代基的芳香醇、2-噻吩甲醇、α,β-不饱和醇与环状脂肪醇等的直接脱氢反应均具有较好催化性能.HT表面的Pd(Ⅱ)物种反应后转变为平均粒径为2.0～2.5nm的Pd纳米粒于或纳米簇.具有较高分散度的Pd(Ⅱ)物种易转变为较小的Pd纳米粒子,从而具有较佳的催化性能.本文推测,催化剂表面的碱性位可促进苯甲醇O-H键的活化,形成Pd-苯甲氧基中间体,该中间体进一步脱氢生成苯甲醛和Pd-H物种;而催化剂表面的质子酸位可与Pd-H作用,促进H2的脱除.
参考文献
| [1] | Mallat T;Baiker A .[J].Chemical Reviews,2004,104:3037. |
| [2] | Mori, K;Hara, T;Mizugaki, T;Ebitani, K;Kaneda, K .Hydroxyapatite-supported palladium nanoclusters: A highly active heterogeneous catalyst for selective oxidation of alcohols by use of molecular oxygen[J].Journal of the American Chemical Society,2004(34):10657-10666. |
| [3] | 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. |
| [4] | Matsumoto T;Ueno M;Wang N;Kobayashi S .[J].Chemistry-An Asian Journal,2008,3:196. |
| [5] | 何林,倪吉,孙浩,曹勇.精细化学品绿色合成中的纳米Au催化：机遇与挑战[J].催化学报,2009(09):958-964. |
| [6] | Wang T;Shou H;Kou Y;Liu H C .[J].Green Chemistry,2009,11:562. |
| [7] | Hayashi M;Yamada K;Nakayama S;Hayashi H Yamazaki S .[J].Green Chemistry,2000,2:257. |
| [8] | Keresszegi C;Mallat T;Baiker A .[J].New Journal of Chemistry,2001,25:1163. |
| [9] | Zaccheria F;Ravasio N;Psaro R;Fusi A.[J].Chemical Communications,2001:253. |
| [10] | Karvembu R;Prabhakaran;Senthilkumar K;Viswanathamurthi P Natarajan K .[J].Reaction Kinetics and Catalysis Letters,2005,86:211. |
| [11] | 宋伟,师瑞娟,刘俊龙,展恩胜,李占双,徐奕德,申文杰.CeO2负载的Cu,Ir和Pd催化剂上的醇转移脱氢反应[J].催化学报,2007(02):106-108. |
| [12] | Friedrich A;Schneider S .[J].ChemCatChem,2009,1:72. |
| [13] | Choi J H;Kim N;Shin Y J;Park J H Park J .[J].Tetrahedron Letters,2004,45:4607. |
| [14] | Kim WH;Park IS;Park J .Acceptor-free alcohol dehydrogenation by recyclable ruthenium catalyst[J].Organic letters,2006(12):2543-2545. |
| [15] | Mitsudome T;Mikami Y;Funai H;Mizugaki T,Jitsukawa K,Kaneda K .[J].Angewandte Chemie International Edition,2008,47:138. |
| [16] | Mitsudome T;Mikami Y;Ebata K;Mizugaki T;Jitsukawa K;Kaneda K .Copper nanoparticles on hydrotalcite as a heterogeneous catalyst for oxidant-free dehydrogenation of alcohols[J].Chemical communications,2008(39):4804-4806. |
| [17] | Shimizu K;Sugino K;Sawabe K;Satsuma A .[J].Chemistry-A European Journal,2009,15:2341. |
| [18] | Fang, WH;Zhang, QH;Chen, J;Deng, WP;Wang, Y .Gold nanoparticles on hydrotalcites as efficient catalysts for oxidant-free dehydrogenation of alcohols[J].Chemical communications,2010(9):1547-1549. |
| [19] | Wu H L;Zhang Q H;Wang Y .[J].Advanced Synthesis and Catalysis,2005,347:1356. |
| [20] | Li F;Zhang QH;Wang Y .Size dependence in solvent-free aerobic oxidation of alcohols catalyzed by zeolite-supported palladium nanoparticles[J].Applied Catalysis, A. General: An International Journal Devoted to Catalytic Science and Its Applications,2008(1/2):217-226. |
| [21] | Chen J;Zhang QH;Wang Y;Wan HL .Size-dependent catalytic activity of supported palladium nanoparticles for aerobic oxidation of alcohols[J].Advanced synthesis & catalysis,2008(3):453-464. |
| [22] | Ebitani K;Motokura K;Mori K;Mizugaki T;Kaneda K .Reconstructed hydrotalcite as a highly active heterogeneous base catalyst for carbon-carbon bond formations in the presence of water[J].The Journal of Organic Chemistry,2006(15):5440-5447. |
| [23] | Rakai A;Tessier D;Bozon-Verduraz F .[J].New Journal of Chemistry,1992,16:869. |
| [24] | Boily JF;Seward TM .Palladium(II) chloride complexation: Spectrophotometric investigation in aqueous solutions from 5 to 125 degrees C and theoretical insight into Pd-Cl and Pd-OH2 interactions[J].Geochimica et Cosmochimica Acta: Journal of the Geochemical Society and the Meteoritical Society,2005(15):3773-3789. |
| [25] | Grunwaldt J D;Caravati M;Baiker A .[J].Journal of Physical Chemistry B,2006,110:25586. |
| [26] | Kovtun G;Kameneva T;Hladyi S;Starchevsky M Pazdersky Y Stolarov I Vargaftik M Moiseev I .[J].Advanced Synthesis and Catalysis,2002,344:957. |
| [27] | Ebitani K;Fujie Y;Kaneda K .[J].Langmuir,1999,15:3557. |
| [28] | Choi KM.;Akita T.;Mizugaki T.;Ebitani K.;Kaneda K. .Highly selective oxidation of allylic alcohols catalysed by monodispersed 8-shell Pd nanoclusters in the presence of molecular oxygen[J].New Journal of Chemistry,2003(2):324-328. |
| [29] | Kakiuchi N;Maeda Y;Nishimura T;Uemura S .[J].Journal of Organic Chemistry,2001,66:6620. |
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