A Pd nanocatalyst supported on multifaceted mesoporous silica with enhanced activity and stability for glycerol electrooxidation

被引:21
作者
Almeida, Thiago S. D. [1 ]
Guima, Katia-Emiko [1 ]
Silveira, Roberto M. [2 ,3 ]
da Silva, Gabriel C. [4 ]
Martines, Marco A. U. [2 ]
Martins, Caue A. [1 ]
机构
[1] Fundacao Univ Fed Grande Dourados, Fac Exact Sci & Technol, BR-79804970 Dourados, MS, Brazil
[2] Univ Fed Mato Grosso do Sul, Inst Chem, CP 549, BR-79070900 Campo Grande, MS, Brazil
[3] Inst Fed Educ Ciencia & Tecnol Mato Grosso Sul, Campus Ponta Pora, BR-79900000 Ponta Pora, MS, Brazil
[4] Univ Sao Paulo, Inst Quim Sao Carlos, IQSC USP, CP 780, Sao Carlos, SP, Brazil
关键词
ONE-POT SYNTHESIS; MEDIATED SYNTHESIS; ALCOHOL OXIDATION; FUEL-CELLS; PALLADIUM; NANOPARTICLES; PLATINUM; NANOCRYSTALS; GRAPHENE; METHANOL;
D O I
10.1039/c6ra28864b
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Glycerol is massively produced as a byproduct of biodiesel manufacturing, which decreases its price and increases its inadequate disposal. The use of glycerol to feed anodes of alkaline fuel cells and electrolysers has emerged as potential alternatives for its use. However, the activity and stability of commercial Pd/C nanoparticles currently proposed do not reach the required performance. Here, we propose a new Pd catalyst deposited in mesoporous silica (SiO2) with enhanced activity and stability for glycerol electrooxidation in alkaline media. We synthesized well- ordered mesoporous silica with pores in the form of a fountain pen and lm (3) over barm symmetry, in a cage-like arrangement. Such a structure was proved by experiments of microscopy, X-ray diffraction, N-2 isotherms and small-angle X-ray scattering measured in synchrotron light. Next, we produced patterned Pd/SiO2 in a one-step synthesis and ordered Pd after template removal. The Pd catalysts were characterized by microscopy, dispersive X-ray spectrometry and X-ray diffraction. Pd/SiO2 and Pd showed improved current density and stability compared to Pd/C. The current density of Pd/SiO2 reached twice the values found for Pd/C. The enhancement is understood as a multiple role of the mesoporous silica support, which works as a seed mediator to order the Pd nanoparticles and mainly as a trap that confines the reactant inside the mesoporous structure, increasing the frequency of collision with active Pd sites. Furthermore, we showed that no carbonyl or intact glycerol was found on Pd/SiO2 after exhaustive cycles of use, except for adsorbed CO that was quickly removed from the surface, which is a probable reason for an improved pathway of glycerol electrooxidation via CO.
引用
收藏
页码:12006 / 12016
页数:11
相关论文
共 46 条
[1]   Nickel/mesoporous silica (SBA-15) modified electrode: An effective porous material for electrooxidation of methanol [J].
Azizi, Seyed Naser ;
Ghasemi, Shahram ;
Chiani, Elham .
ELECTROCHIMICA ACTA, 2013, 88 :463-472
[2]   Influence of synthesis temperature on morphology of SBA-16 mesoporous materials with a three-dimensional pore system [J].
Ballem, Mohamed A. ;
Cordoba, Jose M. ;
Oden, Magnus .
MICROPOROUS AND MESOPOROUS MATERIALS, 2010, 129 (1-2) :106-111
[3]   PHENOMENOLOGICAL ASPECTS RELATED TO THE ELECTROCHEMICAL-BEHAVIOR OF SMOOTH PALLADIUM ELECTRODES IN ALKALINE-SOLUTIONS [J].
BOLZAN, AE .
JOURNAL OF ELECTROANALYTICAL CHEMISTRY, 1995, 380 (1-2) :127-138
[4]  
Brinker CJ, 2013, SOL GEL SCI PHYS CHE
[5]   On a theory of the van der Waals adsorption of gases [J].
Brunauer, S ;
Deming, LS ;
Deming, WE ;
Teller, E .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1940, 62 :1723-1732
[6]   Polymer-mediated synthesis of highly dispersed Pt nanoparticles on carbon black [J].
Chen, M ;
Xing, YC .
LANGMUIR, 2005, 21 (20) :9334-9338
[7]   One-step electrochemical synthesis of preferentially oriented (111) Pd nanocrystals supported on graphene nanoplatelets for formic acid electrooxidation [J].
Chen, Qing-Song ;
Xu, Zhong-Ning ;
Peng, Si-Yan ;
Chen, Yu-Min ;
Lv, Dong-Mei ;
Wang, Zhi-Qiao ;
Sun, Jing ;
Guo, Guo-Cong .
JOURNAL OF POWER SOURCES, 2015, 282 :471-478
[8]   Electro-oxidation of ethylene glycol and glycerol at palladium-decorated FeCo@Fe core-shell nanocatalysts for alkaline direct alcohol fuel cells: functionalized MWCNT supports and impact on product selectivity [J].
Fashedemi, Omobosede O. ;
Miller, Hamish A. ;
Marchionni, Andrea ;
Vizza, Francesco ;
Ozoemena, Kenneth I. .
JOURNAL OF MATERIALS CHEMISTRY A, 2015, 3 (13) :7145-7156
[9]   Establishing a Link between Well-Ordered Pt(100) Surfaces and Real Systems: How Do Random Superficial Defects Influence the Electro-oxidation of Glycerol? [J].
Fernandez, Pablo S. ;
Gomes, Janaina Fernandes ;
Angelucci, Camilo A. ;
Tereshchuk, Polina ;
Martins, Caue A. ;
Camara, Giuseppe A. ;
Martins, Maria E. ;
Da Silva, Juarez L. F. ;
Tremiliosi-Filho, Germano .
ACS CATALYSIS, 2015, 5 (07) :4227-4236
[10]   Evidence for Independent Glycerol Electrooxidation Behavior on Different Ordered Domains of Polycrystalline Platinum [J].
Fernandez, Pablo S. ;
Martins, Caue A. ;
Angelucci, Camilo A. ;
Gomes, Janaina F. ;
Camara, Giuseppe A. ;
Martins, Maria E. ;
Tremiliosi-Filho, Germano .
CHEMELECTROCHEM, 2015, 2 (02) :263-268