Influence of Pd and Au on electrochemical valorization of glycerol over Ni-rich surfaces

Houache, Mohamed S. E.; Shubair, Asma; Sandoval, Mario G.; Safari, Reza; Botton, Gianluigi A.; Jasen, Paula Verónica; Gonzalez, Estela Andrea; Baranova, Elena A.

doi:10.1016/j.jcat.2021.02.008

Cited by 20 publications

(22 citation statements)

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“…Ni‐based mono‐ and bimetallic (NiBi, NiB, NiCu, NiFe, NiCo, NiPd, NiAu, NiCoO 2 ) electrocatalysts have been investigated in the three‐electrode electrochemical cell, 15‐23 while device tests in an electrolyser are less frequently investigated 15,21‐23 . Bimetallic catalysts have improved catalytic activity compared to monometallic Ni.…”

Section: Introductionmentioning

confidence: 99%

Electrolysis of glycerol to value‐added chemicals in alkaline media

Shubair

Houache

et al. 2022

J of Chemical Tech & Biotech

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BACKGROUND Glycerol, a by‐product of biodiesel production, is produced in large quantities, exceeding its demand. The saturation of glycerol resulted in a sharp reduction in its market value and the surplus waste may pose a risk to the environment. By means of electrochemical technologies, glycerol could be oxidized into value‐added products such as glycerate, tartronate and lactate. In the present work, carbon‐supported NiBi catalysts with different atomic ratios (NixBi1−x/C, wherex = 100, 95, 90 and 50 at%) were fabricated and utilized in a 25 cm2 electrolysis cell. RESULTS The as‐fabricated catalysts were characterized and analyzed by various physicochemical and electrochemical characterizations. Using a three‐electrode electrochemical cell, Ni95Bi5/C showed the highest current density of 104 mA cm−2, with an onset potential of 1.32 V versus a reversible hydrogen electrode. Long‐term chronoamperometry was performed in a glycerol electrolysis cell accompanied by the product analysis using high‐performance liquid chromatography. It was found that Ni95Bi5/C had higher selectivity to glycerate C3 product compared to Ni/C. Additionally, optimizing experimental conditions (applied potential, residence time and temperature) to achieve higher selectivity to C3 products was thoroughly studied. The selectivity to C3 value‐added products was enhanced by adjusting the operating conditions. CONCLUSION Small addition of bismuth to Ni/C enhanced both catalytic activity and selectivity to C3 products. The main products formed on NixBi1−x/C were formate and glycerate, while the secondary products were glycolate, tartronate, oxalate and lactate. By running electrolysis under optimal conditions, the selectivity to C3 products was significantly enhanced. © 2022 Society of Chemical Industry (SCI).

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Section: Introductionmentioning

confidence: 99%

Electrolysis of glycerol to value‐added chemicals in alkaline media

Shubair

Houache

et al. 2022

J of Chemical Tech & Biotech

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“…[2] Therefore, many of these catalysts yield formate with high selectivity. [3][4][5] Despite the efforts to increase the selectivity to value-added products such as glyceric acid, either conversion is strongly limited, or the selectivity to other products involving CÀ C cleavage is high. [4,6] Aiming at an increase of the selectivity of glyceric acid/ glycerate from glycerol oxidation, we were inspired by the work of Kim et al, [7] who protected the aldehyde group of 5-(hydroxymethyl)furfural (HMF) using ethylene glycol to form a cyclic acetal.…”

Section: Introductionmentioning

confidence: 99%

“…[3][4][5] Despite the efforts to increase the selectivity to value-added products such as glyceric acid, either conversion is strongly limited, or the selectivity to other products involving CÀ C cleavage is high. [4,6] Aiming at an increase of the selectivity of glyceric acid/ glycerate from glycerol oxidation, we were inspired by the work of Kim et al, [7] who protected the aldehyde group of 5-(hydroxymethyl)furfural (HMF) using ethylene glycol to form a cyclic acetal. Likewise, two vicinal glycerol hydroxyl groups can be protected by acetalization with acetone yielding the prospective green solvent solketal (isopropylidene glycerol) over suitable acidic catalysts as shown in Scheme 1.…”

Section: Introductionmentioning

confidence: 99%

“…Therefore, many of these catalysts yield formate with high selectivity [3–5] . Despite the efforts to increase the selectivity to value‐added products such as glyceric acid, either conversion is strongly limited, or the selectivity to other products involving C−C cleavage is high [4,6] …”

Section: Introductionmentioning

confidence: 99%

“…However, non‐noble metal‐based electrocatalysts, which are preferably used due to their lower cost and higher abundance, have a strong tendency for C−C cleavage [2] . Therefore, many of these catalysts yield formate with high selectivity [3–5] . Despite the efforts to increase the selectivity to value‐added products such as glyceric acid, either conversion is strongly limited, or the selectivity to other products involving C−C cleavage is high [4,6] …”

Section: Introductionmentioning

confidence: 99%

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Selective Anodic Oxidation of Solketal as Acetal‐Protected Glycerol over Nickel Boride in Alkaline Media to Glyceric Acid**

Cychy

Lechler

2021

ChemElectroChem

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Alkaline anodic oxidation of glycerol suffers from facile C−C bond cleavage, especially when using non‐precious metal electrocatalysts, which limits the yield of more valuable C3 oxygenates. Usually, a high C3 selectivity is a tradeoff with conversion for most catalysts. Thus, we used solketal as the reactant, which is acetal‐protected glycerol with acetone. CV experiments showed that solketal is oxidized over nickel boride (NixB) at potentials where NiOOH is formed. Electrolysis over NixB in a thin‐film spectroelectrochemical flow cell at 1.58 V vs. RHE to avoid pronounced oxygen evolution showed a stable current density of ca. 6 mA cm−2. Simultaneously recorded ATR‐FTIR spectra revealed solketal conversion to solketalate and formate. Indeed, 59 % conversion and 77 % selectivity to glyceric acid were determined by HPLC after acidic cleavage of the acetal, resulting in a yield of 45 %. Therefore, solketal is a promising reactant for the selective electrosynthesis of glyceric acid.

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Clarifying Glycerol Electrooxidation Studies on Pd‐Based Catalysts: Insights Into Catalytic Performance and Practical Challenges

Zanata,

Alencar,

Santos

et al. 2024

ChemPlusChem

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Escalating biodiesel production led to a surplus of glycerol, prompting its exploration as a valuable resource in industrial applications. Electrochemical systems have been studied, specifically employing noble metal catalysts like palladium for glycerol electrooxidation. Despite numerous studies on Pd‐based catalysts for glycerol electrooxidation, a comprehensive analysis addressing critical questions related to the economic feasibility, global sourcing of Pd, and the thematic cohesion of publications in this field is lacking. Moreover, a standardized framework for comparing the results of various studies is absent, hindering progress on glycerol technologies. This critical overview navigates the evolution of Pd‐based catalysts for glycerol electrooxidation, examining catalytic activity, stability, and potential applications. It critically addresses the geographical sources of Pd, the motivation behind glycerol technology exploration, thematic coherence in existing publications, and the meaningful comparison of results. It correlates the use of Pd‐based catalysts with the natural source of Pd and the origin of glycerol derived from biodiesel. The proposed standardized approach for comparing electrochemical parameters and establishing experimental protocols provides a foundation for meaningful study comparisons. This critical overview underscores the need to address fundamental questions to accelerate the transition of glycerol technologies from laboratories to practical applications.

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Influence of Pd and Au on electrochemical valorization of glycerol over Ni-rich surfaces

Cited by 20 publications

References 50 publications

Electrolysis of glycerol to value‐added chemicals in alkaline media

Electrolysis of glycerol to value‐added chemicals in alkaline media

Selective Anodic Oxidation of Solketal as Acetal‐Protected Glycerol over Nickel Boride in Alkaline Media to Glyceric Acid**

Clarifying Glycerol Electrooxidation Studies on Pd‐Based Catalysts: Insights Into Catalytic Performance and Practical Challenges

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