Electrochemistry for biofuels waste valorization: Vinasse as a reducing agent for Pt/C and its application to the electrolysis of glycerin and vinasse

Crisafulli, Rudy; Amorim, Fernando M. de Lino; Marcionilio, Suzana Maria Loures de Oliveira; Cunha, William Mendes; Araújo, Brenda R.S. de; Dias, José A.; Linares, J.

doi:10.1016/j.elecom.2019.03.012

Cited by 9 publications

(7 citation statements)

References 27 publications

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“…In other words, the organic molecule behaves as a strong depolarizing agent, allowing for the production of H 2 in a range of electrical potentials where water electrolysis is not thermodynamically possible. Some of the most representative examples of this technology are the electrolysis of glycerol, [3][4][5]11,12 vinasse 13 and lignin, [6][7][8][14][15][16][17][18][19] being massive by-products of the bio-diesel production process, the fermentation process in the sugarcane industry, and the Kraft-paper industry, respectively.…”

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confidence: 99%

Towards Understanding Lignin Electrolysis: Electro-Oxidation of a β-O-4 Linkage Model on PtRu Electrodes

Beliaeva

Elsheref

Walden

et al. 2020

J. Electrochem. Soc.

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The reaction mechanism for lignin electrolysis has been rarely studied. In a previous work, we reported the electrolysis of lignin on a Polymer Electrolyte Membrane (PEM) alkaline electrolyzer with PtRu-based anodes. Even though the performance of this technology was proven in a low range of applied potentials (< 1.2 V) and reaction temperatures (< 90 o C), the activity of the system was strongly hindered, leading to low H2 production rates. The aim of this work is to study the main limitations of PtRu electrodes for lignin electro-oxidation. 2-Phenoxyethanol, 2-PE, has been chosen as a model molecule of the b-O-4 linkage, which represents ≈ 60 % of the lignin bio-polymer. The performed electrochemical experiments, together with the HPLC analysis of the anodic products and the thermodynamic DFT computations, suggest that the electro-oxidation of the 2-PE organic molecule is very limited and leads to the production of the carboxylic acid as the final reaction product. In addition, the electro-catalytic system was severely poisoned, probably owing to the presence of some reaction by-products. All in all, this study allows advancing one step-forward towards understanding the reaction mechanism and the main limitations of the lignin electrolysis technology in the above described system.

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confidence: 99%

Towards Understanding Lignin Electrolysis: Electro-Oxidation of a β-O-4 Linkage Model on PtRu Electrodes

Beliaeva

Elsheref

Walden

et al. 2020

J. Electrochem. Soc.

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“…For instance, at a mass-normalized current density of 1 mA mg Pd −1 , the potential for GEOR is −0.015 V vs. NHE, whereas for the OER the corresponding value is 0.82 V vs. NHE. Such differences are responsible for the reduced energy demand of the glycerol electrochemical reforming compared to water electrolysis [49], as already observed for ethanol electrolysis [50][51][52]. Figure 2 also displays the HER, showing a very low overpotential typical of this low-polarizable process [53].…”

Section: Resultsmentioning

confidence: 54%

“…Nanomaterials 2022, 12, x FOR PEER REVIEW 6 of 13 mA mgPd −1 , the potential for GEOR is −0.015 V vs. NHE, whereas for the OER the corresponding value is 0.82 V vs. NHE. Such differences are responsible for the reduced energy demand of the glycerol electrochemical reforming compared to water electrolysis [49], as already observed for ethanol electrolysis [50][51][52]. Figure 2 shows the corresponding voltammogram for GEOR and OER in NaOH (Figure 2 (left)), and for HER in H 2 SO 4 (Figure 2(right)).…”

Section: Resultsmentioning

confidence: 55%

An Alkaline-Acid Glycerol Electrochemical Reformer for Simultaneous Production of Hydrogen and Electricity

2022

Self Cite

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This study shows the results, for the first time, of an glycerol alkaline-acid electrolyzer. Such a configuration allows spontaneous operation, producing energy and hydrogen simultaneously as a result of the utilization of the neutralization and fuel chemical energy. The electroreformer—built with a 20 wt% Pd/C anode and cathode, and a Na+-pretreated Nafion® 117—can simultaneously produce hydrogen and electricity in the low current density region, whereas it operates in electrolysis mode at high current densities. In the spontaneous region, the maximum power densities range from 1.23 mW cm−2 at 30 °C to 11.9 mW cm−2 at 90 °C, with a concomitant H2 flux ranging from 0.0545 STP m−3 m−2 h−1 at 30 °C to 0.201 STP m−3 m−2 h−1 at 90 °C, due to the beneficial effect of the temperature on the performance. Furthermore, over a chronoamperometric test, the electroreformer shows a stable performance over 12 h. As a challenge, proton crossover from the cathode to the anode through the cation exchange Nafion® partially reduces the pH gradient, responsible for the extra electromotive force, thus requiring a less permeable membrane.

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“…3 The GEOR is a complex process involving various intermediates and products. 13,14 So far, numerous studies have been dedicated to exploring promising catalysts and understanding GEOR mechanisms and pathways on noble metalbased nanoparticles (NPs) and structures 15 like pure platinum (Pt/C, 16 Pt/CNT, 17,18 and Pt(111) and Pt(100) 19 ), palladium (Pd NPs, 20 Pd/CNT 17,21 ), gold (Au/CNT, 17,22 Au film, 23 Au NPs, 24 Au(111) 25 ), bi-and trimetallic alloys (AuPt, 26 PtCu/ C, 27 PtPdM (M = Ni, Fe, Co) nanosheets, 28 PdAg/CNT, 29 PdNi, 30 Pt on MoO x nanosheets 31 ) and transition metal-based catalysts like NiBi, 32 CoMoO 4 , 33 CuCo 2 O 4 , 34 and ZnFe x Co 2−x O 4 . 35 It is well-known that Pt-based catalysts possess high catalytic activity; however, one of the promising metallic catalysts that can compete with Pt is Pd.…”

Section: Introductionmentioning

confidence: 99%

“…Therefore, transforming this renewable biomass derivative into commercially added-value chemicals is considered very promising. , Glycerol can be converted into many valuable products, primarily through the catalytic oxidation of hydroxyl groups. , Among the various approaches, the glycerol electrochemical oxidation reaction (GEOR) provides not only a way to produce valuable chemicals from glycerol but also a less energetically demanding concurrent hydrogen generation on the cathode, compared to conventional water electrolysis . The GEOR is a complex process involving various intermediates and products. , So far, numerous studies have been dedicated to exploring promising catalysts and understanding GEOR mechanisms and pathways on noble metal-based nanoparticles (NPs) and structures like pure platinum (Pt/C, Pt/CNT, , and Pt(111) and Pt(100)), palladium (Pd NPs, Pd/CNT , ), gold (Au/CNT, , Au film, Au NPs, Au(111)), bi- and trimetallic alloys (AuPt, PtCu/C, PtPdM (M = Ni, Fe, Co) nanosheets, PdAg/CNT, PdNi, Pt on MoO x nanosheets) and transition metal-based catalysts like NiBi, CoMoO 4 , CuCo 2 O 4 , and ZnFe x Co 2– x O 4 . It is well-known that Pt-based catalysts possess high catalytic activity; however, one of the promising metallic catalysts that can compete with Pt is Pd …”

Section: Introductionmentioning

confidence: 99%

Electrocatalytic Oxidation of Glycerol to Value-Added Compounds on Pd Nanocrystals

Terekhina

White

Cornell

et al. 2023

ACS Appl. Nano Mater.

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Pd octahedral, rhombic dodecahedral, and cubic nanoparticles (PdOCTA, PdRD, and PdCUBE NPs) were synthesized, characterized, and studied as catalysts for the glycerol electrooxidation reaction (GEOR) in a strongly alkaline medium at 20 and 60 °C. The highest mass activity of 0.050 and 0.183 mA/μgPd was observed on PdOCTA at 20 and 60 °C, respectively, whereas PdCUBE exhibited the highest specific activity of 1.49 and 12.84 mA/cmPd 2, respectively. The GEOR products were analyzed by high-performance liquid chromatography (HPLC), and their selectivity and overall glycerol conversion were evaluated at 0.86 V vs RHE. The selectivity toward the three-carbon chain (C3) GEOR products was similar for the different types of catalysts, with PdOCTA and PdCUBE NPs achieving more than 50% selectivity at 20 °C and more than 60% at 60 °C. Glycerate was the overall dominant product for all catalysts, with a selectivity of up to 42%. The glycerol conversion was found to be highest for PdOCTA21% at 20 °C and 82% at 60 °C, while PdRD was the least active and showed less than 3% conversion at 20 °C and 35% at 60 °C. Based on the GEOR product distribution, a reaction mechanism was proposed.

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Electrochemistry for biofuels waste valorization: Vinasse as a reducing agent for Pt/C and its application to the electrolysis of glycerin and vinasse

Cited by 9 publications

References 27 publications

Towards Understanding Lignin Electrolysis: Electro-Oxidation of a β-O-4 Linkage Model on PtRu Electrodes

Towards Understanding Lignin Electrolysis: Electro-Oxidation of a β-O-4 Linkage Model on PtRu Electrodes

An Alkaline-Acid Glycerol Electrochemical Reformer for Simultaneous Production of Hydrogen and Electricity

Electrocatalytic Oxidation of Glycerol to Value-Added Compounds on Pd Nanocrystals

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