Effects of carbon support on glycerol oxidation over Pt-C composite catalysts in base-free conditions

doi:10.11949/j.issn.0438-1157.20161026

Abstract

Abstract:

Activated carbon (AC) and carbon nanotubes (CNTs) supported Pt catalysts with similar particle sizes prepared by incipient wetness impregnation method were used for study of base-free oxidation of glycerol. The results showed that carbon support of Pt-C composite catalysts had significant impact on reactivity, selectivity, and steady state of glycerol oxidation. Compared to Pt/CNTs catalyst, Pt/AC catalyst had a lower binding energy of Pt 4f leading to a higher oxygen coverage on catalyst surface which reduced glycerol adsorption and initial activity of glycerol oxidation. Pt/AC catalyst further favored oxidation of glyceraldehyde to glyceric acid and C-C bond cleavage of C₃ products. With regards to catalyst deactivation, oxygen poison and adsorption of intermediates were main factors to Pt/AC catalyst while blockage of Pt active sites by adsorption of glyceric acid was a significant contributor to Pt/CNTs catalyst.

Key words: glycerol, oxidation, Pt-C composite, support, deactivation

摘要：

采用等量浸渍法制备了具有相似平均粒径的活性炭（AC）和碳纳米管（CNTs）负载的Pt催化剂，并比较研究了非碱性条件下两种催化剂催化甘油氧化反应的性能。结果表明，炭载体对Pt-C复合物催化甘油氧化反应的活性、选择性和稳定性有重要影响。相对于Pt/CNTs催化剂，Pt/AC催化剂中Pt 4f结合能较低，导致其表面氧的覆盖度相对较高，因而抑制了甘油的吸附，降低了甘油氧化反应的初始活性；Pt/AC催化剂会促进甘油醛进一步氧化成甘油酸以及C₃产物的氧化断键；Pt/AC催化剂失活的主要原因是氧中毒和中间产物的吸附，而Pt/CNTs催化剂的失活主要是由于甘油酸的吸附堵塞Pt表面的活性位造成的。

关键词: 甘油, 氧化, Pt-C复合物, 载体, 失活

CLC Number:

TQ203.2

LEI Jiaqi, DUAN Xuezhi, QIAN Gang, ZHOU Xinggui. Effects of carbon support on glycerol oxidation over Pt-C composite catalysts in base-free conditions[J]. CIESC Journal, 2017, 68(2): 679-686.

雷佳契, 段学志, 钱刚, 周兴贵. 炭载体对Pt-C复合物非碱性条件下催化甘油氧化性能的影响[J]. 化工学报, 2017, 68(2): 679-686.

References 31

[1]	HUBER G W, IBPRRA S, CORMA A. Synthesis of transportation fuels from biomass:chemistry, catalysts, and engineering[J]. Chem. Rev., 2006, 106(9):4044-4098.
[2]	BEHR A, EILTING J, IRAWADI K, et al. Improved utilisation of renewable resources:new important derivatives of glycerol[J]. Green Chem., 2008, 10(1):13-30.
[3]	CZERNIK S, FRENCH R, FEIK C, et al. Hydrogen by catalytic steam reforming of liquid byproducts from biomass thermoconversion processes[J]. Ind. Eng. Chem. Res., 2002, 41:4209-4215.
[4]	ZHOU C H, BELTRAMINI N J, FAN Y X, et al. Chemoselective catalytic conversion of glycerol as a biorenewable source to valuable commodity chemicals[J]. Chem. Soc. Rev., 2008, 37(3):527-549.
[5]	KATRYNIOK B, KIMURA H, SKRZYNSKA E, et al. Selective catalytic oxidation of glycerol:perspectives for high value chemicals[J]. Green Chem., 2011, 13(8):1960-1979.
[6]	DAVIS W R, TOMSHO J, NIKAM S, et al. Inhibition of HIV-1 reverse transcriptase-catalyzed DNA strand transfer reactions by 4-chlorophenylhydrazone of mesoxalic acid[J]. Biochemistry, 2000, 39(46):14279-14291.
[7]	KIMURA H, TSUTO K. Catalytic synthesis of DL-serine and glycine from glycerol[J]. J. Am. Oil Chem. Soc., 1993, 70(10):1027-1030.
[8]	ZOPE B N, HIBBITTS D D, NEUROCK M, et al. Reactivity of the gold/water interface during selective oxidation catalysis[J]. Science, 2010, 330(6000):74-78.
[9]	VILLA A, VEITH G M, PRATI L. Selective oxidation of glycerol under acidic conditions using gold catalysts[J]. Angew. Chem. Int. Ed., 2010, 49(26):4499-4502.
[10]	TSUJI A, RAO K T V, NISHIMURA S, et al. Selective oxidation of glycerol by using a hydrotalcite-supported platinum catalyst under atmospheric oxygen pressure in water[J]. ChemSusChem, 2011, 4(4):542-548.
[11]	LIU S S, SUN K Q, XU B Q. Specific selectivity of Au-catalyzed oxidation of glycerol and other C3-polyols in water without the presence of a base[J]. ACS Catal., 2014, 4(7):2226-2230.
[12]	YUAN Z F, GAO Z K, XU B Q. Acid-base property of the supporting material controls the selectivity of Au catalyst for glycerol oxidation in base-free water[J]. Chinese J. Catal., 2015, 36(9):1543-1551.
[13]	BRETT G L, HE Q, HAMMOND C, et al. Selective oxidation of glycerol by highly active bimetallic catalysts at ambient temperature under base-free conditions[J]. Angew. Chem. Int. Ed., 2011, 50(43):10136-10139.
[14]	HIRASAWA S, WATANABE H, KIZUKA T, et al. Performance, structure and mechanism of Pd-Ag alloy catalyst for selective oxidation of glycerol to dihydroxyacetone[J]. J. Catal., 2013, 300:205-216.
[15]	GARCIA R, BESSON M, GALLEZOT P. Chemoselective catalytic oxidation of glycerol with air on platinum metals[J]. Appl. Catal. A:Gen., 1995, 127(1/2):165-176.
[16]	LEI J Q, DUAN X Z, QIAN G, et al. Size effects of Pt nanoparticles supported on carbon nanotubes for selective oxidation of glycerol in a base-free condition[J]. Ind. Eng. Chem. Res., 2014, 53(42):16309-16315.
[17]	LEI J Q, DUAN X Z, QIAN G, et al. Insights into activated carbon-supported platinum catalysts for base-free oxidation of glycerol[J]. Ind. Eng. Chem. Res., 2016, 55(2):420-427.
[18]	RODRIGUES E G, PEREIRA M F, CHEN X W, et al. Selective oxidation of glycerol over platinum-based catalysts supported on carbon nanotubes[J]. Ind. Eng. Chem. Res., 2013, 52(49):17390-17398.
[19]	GAO J, LIANG D, CHEN P, et al. Oxidation of glycerol with oxygen in a base-free aqueous solution over Pt/AC and Pt/MWNTs catalysts[J]. Catal. Lett., 2009, 130(1/2):185-191.
[20]	DAN L, GAO J, WANG J H, et al. Selective oxidation of glycerol with oxygen in a base-free aqueous solution over MWNTs supported Pt catalysts[J]. Appl. Catal. B:Environ., 2011, 106:423-432.
[21]	SERP P, CORRIAS M, KALCK P. Carbon nanotubes and nanofibers in catalysis[J]. Appl. Catal. A:Gen., 2003, 253(2):337-358.
[22]	ROY A K, HSIEH C T. Pulse microwave-assisted synthesis of Pt nanoparticles onto carbon nanotubes as electrocatalysts for proton exchange membrane fuel cells[J]. Electrochimica Acta, 2013, 87:63-72.
[23]	ZENG J H, SU F B, LEE J Y, et al. Method for preparing highly dispersed Pt catalysts on mesoporous carbon support[J]. J. Mater. Sci., 2007, 42:7191-7197.
[24]	ZHANG M Y, NIE R F, WANG L, et al. Selective oxidation of glycerol over carbon nanofibers supported Pt catalysts in a base-free aqueous solution[J]. Chem. Commun., 2015, 59:5-9.
[25]	LI Y, ZAERA F. Sensitivity of the glycerol oxidation reaction to the size and shape of the platinum nanoparticles in Pt/SiO2 catalysts[J]. J. Catal., 2015, 326:116-126.
[26]	KNUPP S L, LI W Z, PASCHOS O, et al. The effect of experimental parameters on the synthesis of carbon nanotube/nanofiber supported platinum by polyol processing techniques[J]. Carbon, 2008, 46(10):1276-1284.
[27]	CHEN W Y, JI J, DUAN X Z, et al. Unique reactivity in Pt/CNTs catalyzed hydrolytic dehydrogenation of ammonia borane[J]. Chem. Commun., 2014, 50:2142-2144.
[28]	CARRETTIN S, MCMORN P, JOHNSTON P, et al. Oxidation of glycerol using supported Pt, Pd and Au catalysts[J]. Phys. Chem. Chem. Phys., 2003, 5(6):1329-1336.
[29]	MALLAT T, BAIKER A. Oxidation of alcohols with molecular oxygen on platinum metal catalysts in aqueous solutions[J]. Catal. Today, 1994, 19(2):247-283.
[30]	MARKUSSE A P, KUSTER B F M, KONINGSBERGER D C, et al. Platinum deactivation:in situ EXAFS during aqueous alcohol oxidation reaction[J]. Catal. Lett., 1998, 55(3):141-145.
[31]	BESSON M, GALLEZOT P. Selective oxidation of alcohols and aldehydes on metal catalysts[J]. Catal. Today, 2000, 57:127-141.