Abstract
Biomass is abundant, inexpensive and renewable, therefore, it is highly expected to play a significant role in our future energy and chemical landscapes [1]. Crude glycerol can be coproduced from biodiesel production, and can serve as a primary building block for higher-valued chemical production [2]. In my presentation, I will present our research work in electrocatlytic oxidation of glycerol for cogeneration of valuable chemicals and electricity [3-7]. We investigated electrocatalytic selective oxidation of glycerol and discovered that the degree of glycerol oxidation on Au nanoparticles can be well tuned with anode potential to produce tartronate (oxidizing two primary –OH, ≥ 0.35 V), mesoxalate (oxidizing three –OH, ≥ 0.45 V) or glycolate (breaking C-C bond, ≥ 0.9 V) [3-5]. We then prepared PdAg bimetallic nanoparticle catalyst is more efficient than Pd for alcohol oxidation [6,7]: Pd can facilitate deprotonation of alcohol in a base electrolyte, while Ag can promote intermediate aldehyde oxidation and cleavage of C-C bond of C3 species to C2 species. A primary sequence of electrocatalytic oxidation of glycerol over PdAg catalysts was outlines. We found a combination of the two active sites (Pd and Ag) with two different functions, can simultaneously improve the reaction rates and deeper oxidation products of alcohols. Our recent research on PtAg and AuAg nanoparticle catalysts for glycerol oxidation will also be presented.
References:
1) (a)T.A. Werpy, J.E. Holladay, and J.F. White, Top Value Added Chemicals From Biomass: I. Results of Screening for Potential Candidates from Sugars and Synthesis Gas, 2004. p. Medium: ED; Size: PDFN. (b) J.E. Holladay, J.F. White, J.J. Bozell, and D. Johnson, Top Value-Added Chemicals from Biomass - Volume II—Results of Screening for Potential Candidates from Biorefinery Lignin, 2007.
2) Chemoselective catalytic conversion of glycerol as a biorenewable source to valuable commodity chemicals, Chun-Hui (Clayton) Zhou,Jorge N. Beltramini, Yong-Xian Fan, G. Q. (Max) Lu, Chemical Society Reviews, 2008, 37, 527-569.
3) Le Xin, Zhiyong Zhang, Zhichao Wang, Wenzhen Li, Simultaneous generation of mesoxalic acid and electricity from glycerol on Au anode catalyst in anion exchange membrane fuel cells, ChemCatChem, 2012, 4, 1105-1114
4) Zhiyong Zhang, Le Xin, Ji Qi, David J. Chadderdon, Kai Sun,Kayla M. Warskoa Wenzhen Li, Selective electro-oxidation of glycerol to tartronate or mesoxalate on Au nanoparticle catalyst via electrode potential tuning in anion-exchange membrane electrocatalytic flow reactor, Applied Catalysis B, Environmental, 2014, 147, 871-878.
5) Ji Qi, Le Xin, David J. Chadderdon, Yang Qiu, Yibo Jiang, Neeva Benipal, Changhai Liang, Wenzhen Li, Electrocatalytic selective oxidation of glycerol to tartronate on Au/C anode catalysts in anion exchange membrane fuel cells with electricity cogeneration, Applied Catalysis B, Environmental, 2014, 154–155, 360-368.
6) Ji Qi, Neeva Benipal, Changhai Liang, Wenzhen Li, PdAg/CNT Catalyzed Alcohol Oxidation Reaction for High-Performance Anion Exchange Membrane Direct Alcohol Fuel Cell (Alcohol = Methanol, Ethanol, Ethylene Glycol and Glycerol), Applied Catalysis B: Environmental, 2016,199, 494–503.
7) Neeva Benipal, Ji Qi, Qi Liu, Wenzhen Li, Carbon Nanotube Supported PdAg Nanoparticles for Electrocatalytic Oxidation of Glycerol in Anion Exchange Membrane Fuel Cells, Applied Catalysis B: Environmental, 2017, 210, 121–130.