南京大学学报(自然科学版) ›› 2015, Vol. 51 ›› Issue (2): 310319.
石国军,陈宾宾,许二岗
Shi Guojun, Chen Binbin, Xu Ergang
摘要: 分别以二茂铁和二氧化硅为前驱体和载体,通过“一步法”化学气相沉积来合成Fe2O3/SiO2催化剂.在二茂铁升华温度为110 、载体400 ,N2作为载气,反应气氛为空气,真空度为0.08 MPa的条件下合成出了不同担载量的Fe2O3/SiO2催化剂.同时,以Fe(NO3)3·9H2O为前驱体通过等体积浸渍法制备相同担载量的Fe2O3/SiO2催化剂作为参比催化剂,并用于苯酚羟基化反应以评价其催化活性.通过BET、AAS、HR-TEM、FT-IR、XRD、H2-TPR等手段对催化剂的理化性质进行了表征,以双氧水为氧化剂进行了苯酚羟基化反应.结果表明,通过化学气相沉积合成了高分散的SiO2担载的、高分散的α-Fe2O3纳米颗粒催化剂,活性物种α-Fe2O3纳米颗粒和载体SiO2间存在强相互作用.在反应时间为1 h,反应温度40 ,苯酚与双氧水的摩尔比为1:1,催化剂质量为0.05 g的反应条件下,CVD法制备的0.2 mmol·g的Fe2O3/SiO2催化剂具有最高的反应活性,苯酚转化率为39.16%,邻苯二酚与对苯二酚的选择性分别为59.18%和35.11%.具有相同负载量、浸渍法制备的催化剂没有检测到苯酚的转化.
[1] Esposito A, Neri C, Buonomo F, et al. Process for hydroxylating aromatic hydrocarbons, Italy, GB2116974A. 1983-10-5. [2] Taramasso M, Giovanni P, Notari B. Preparation of porous crystalline synthetic material comprised of silicon and titanium oxides. Italy, GB4410501. 1983-10-18. [3] Zuo Y, Song W, Dai C Y, et al. Modification of small-crystal titanium silicalite-1 with organic bases: Recrystallization and catalytic properties in the hydroxylation of Phenol. Applied Catalysis A: General, 2013, 453: 272~279. [4] Vasile A, Busuioc-Tomoiaga A M. A new route for the synthesis of titanium silicalite-1. Materials Research Bulletin, 2012, 47: 35~41. [5] Tsai S T, Chao P Y, Tsai T C, et al. Effects of pore structure of post-treated TS-1 on phenol hydroxylation. Catalysis Today, 2009, 148: 174~178. [6] Wang X B, Zhang X F, Liu H, et al. Preparation of titanium silicalite-1 catalytic films and application as catalytic membrane reactors. Chemical Engineering Journal, 2010, 156(3): 562~570. [7] Kumar A, Srinivas D. Hydroxylation of phenol with hydrogen peroxide catalyzed by Ti-SBA-12 and Ti-SBA-16. Journal of Molecular Catalysis A: Chemical, 2013, 368: 112~118. [8] Bi J H, Kong L Y, Huang Z X, et al. Self-Encapsulation of [MII(phen)2(H2O)2]2+(M=Co, Zn) in One-Dimensional Nanochannels of [MII(H2O)6(BTC)2]4-(M=Co, Cu, Mn): A High HQ/CAT Ratio Catalyst for Hydroxylation of Phenols. Inorganic Chemistry, 2008, 47(11): 4564~4569. [9] Wang W M, Song J, Han X. Schwertmannite as a new Fenton-like catalyst in the oxidation of phenol by H2O2. Journal of Hazardous Materials, 2013, 262: 412~419. [10] Luca C D, Ivorra F, Massa P, et al. Alumina supported Fenton-like systems for the catalytic wet peroxide oxidation of phenol solutions. Industrial and Engineering Chemistry Research, 2012,51(26): 8979~8984. [11] Santos A, Yustos P, Rodriguez S, et al. Fenton pretreatment in the catalytic wet oxidation of phenol. Industrial and Engineering Chemistry Research, 2010, 49: 5583~5587. [12] Maurya M R, Saklani H,Kumar A, et al. Dioxovanadium(V) complexes of dibasic tridentate ligands encapsulated in zeolite-Y for the liquid phase catalytic hydroxylation of phenol using H2O2 as oxidant. Catalysis Letters, 2004, 93: 1~2. [13] Lin S, Zhen Y, Wang S M, et al. Catalytic activity of K0.5(NH4)5.5 [MnMo9O32]6H2O in phenol hydroxylation with hydrogen peroxide. Journal of Molecular Catalysis A: Chemical, 2000, 156: 113~120. [14] Wang L P, Kong A, Chen B, et al. Direct synthesis, characterization of Cu-SBA-15 and its high catalytic activity in hydroxylation of phenol by H2O2. Journal of Molecular Catalysis A: Chemical, 2005, 230: 143~150. [15] Wang D Y, Liu Z Q, Liu F Q, et al. Fe2O3/Macroporous resin nanocomposites: High efficiency catalysts for hydroxylation of phenol with H2O2. Applied Catalysis A: General, 1998, 174: 25~32. [16] Dong Y L, Niu X Y, Zhu Y J, et al. One-pot synthesis and characterization of Cu-SBA-16 mesoporous molecular sieves as an excellent catalyst for phenol hydroxylation. Catalysis Letters, 2011, 141: 242~250. [17] Lou L L, Liu S X. CuO-containing MCM-48 as catalysts for phenol hydroxylation. Catalysis Communications, 2005, 6: 762~765. [18] Jiang Y Q, Lin K F, Zhang Y N, et al. Fe-MCM-41 nanoparticles as versatile catalysts for phenol hydroxylation and for Friedel–Crafts alkylation. Applied Catalysis A: General, 2012, 445: 172~179. [19] Choi J S , Yoon S S, Jang S H, et al. Phenol hydroxylation using Fe-MCM-41 catalysts. Catalysis Today, 2006, 111: 280~287. [20] Zhao W, Luo Y F, Deng P, et al. Synthesis of Fe-MCM-48 and its catalytic performance in phenol hydroxylation. Catalysis Letters, 2001, 73: 2~4. [21] Shi F W, Zheng J L, Kai Xu, et al. Synthesis of binary Cu–Pd–alginates dry bead and its high catalytic activity for hydroxylation of phenol. Catalysis Communications, 2012, 28: 16~24. [22] Yu R B, Xiao F S, Wang D, et al. Catalytic performance in phenol hydroxylation by hydrogen peroxide over a catalyst of V-Zr-O complex. Catalysis Today, 1999, 51: 39~46. [23] Serp P, Kalck P. Chemical vapor deposition methods for the controlled preparation of supported catalytic materials. Chemical Reviews,2002, 102: 3085~3128. [24] Zhou R, Cao Y, Yan S R, Deng J F, et al. Oxidative dehydrogenation of propane over mesoporous HMS silica supported vanadia. Catalysis Letters, 2001, 75(1): 107~112. [25] Berndt H, Martin A, Bruckner A, et al. Structure and catalytic properties of VOx/MCM materials for the partial oxidation of methane to formaldehyde. Journal of Catalysis, 2000, 191(2): 384~400. [26] Liu Y M, Xu J, He L, et al. Facile synthesis of Fe-loaded mesoporous silica by a combined detemplation-incorporation process through fenton’s chemistry. The Journal of Physical Chemistry C, 2008, 112: 16575~16583. [27] Khalil K M, Mahmoud H A, Ali T T. Direct formation of thermally stabilized amorphous mesoporous Fe2O3/SiO2 nanocomposites by hydrolysis of aqueous iron (III) nitrate in sols of spherical silica particles. Langmuir, 2008, 24: 1037~1043. [28] Guan F F, Yao L F, Xie F J, et al. Optical and magnetic properties of Fe2O3/SiO2 nano-composite films. Journal of Wuhan University of Technology-Mater. Science Edition, 2010, 25(2): 206~209. [29] Rostamizadeh S, Nojavan M, Aryan R, et al. Amino acid-based ionic liquid immobilized on α-Fe2O3-MCM-41: An efficient magnetic nanocatalyst and recyclable reaction media for the synthesis of quinazolin-4(3H)-one derivatives. Journal of Molecular Catalysis A: Chemical, 2013, 374: 102~110. [30] Choi J S, Yoon S S, Jang S H, et al. Phenol hydroxylation using Fe-MCM-41 catalysts. Catalysis Today, 2006, 111: 280~287. [31] Li S P, Wu Q S, Lu G S, et al, Fe-MCM-41 from coal-series kaolin as catalysts for the selective catalytic reduction of NO with ammonia. Journal of Materials Engineering and Performance, 2013, 22: 3762~3768. [32] Zielinski J, Zglinicka I, Znak L, et al. Reduction of Fe2O3 with hydrogen. Applied Catalysis A: General, 2010, 381: 191~196. [33] Valenzuela M A, Bosch P, Becerrill J J, et al. Preparation, characterization and photocatalytic activity of ZnO, Fe2O3 and ZnFe2O4. Journal of Photochemistry and Photobiology A: Chemistry, 2002, 14: 177~182. [34] Liang M S, Kang W K, Xie K C. Comparison of reduction behavior of Fe2O3, ZnO and ZnFe2O4 by TPR technique. Journal of Natural Gas Chemistry, 2009, 18: 110~113. [35] Liu C B, Ye X K, Zhan R Y, et al. Phenol hydroxylation by iron( II) phenanthroline: The reaction Mechanism. Journal of Molecular Catalysis A: Chemical, 1996(112):15~22. [36] Karakhanova E A, Maximov A L, Kardasheva Y S, et al. Copper nanoparticles as active catalysts in hydroxylation of phenol by hydrogen peroxide. Applied Catalysis A: General, 2010, 385: 62~72. [37] Xiong C, Chen Q, Lu W R, et al. Novel Fe-based complex oxide catalysts for hydroxylation of phenol. Catalysis Letters, 2000, 6: 231~236. |
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