Replacing oxygen evolution reaction by glycerol electrooxidation on Rh modified Ni(OH)2/C for energy-efficient hydrogen production

Xavier, Farlon Felipe Silva; Lobo-da-Cunha, Alexandre; Napporn, Têko W.; Olivi, Paulo

doi:10.1016/j.ijhydene.2023.04.267

Cited by 13 publications

(7 citation statements)

References 48 publications

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“…These results, along with those related to mass activity, demonstrate the positive effect of adding Ni on both the electrochemical activity and the mass of Pt used. This can be explained according to three factors: first, the oxophilicity of Ni, which is an inherent property that facilitates the dissociation of water molecules and the formation of oxidized species (principally NiOOH), especially in alkaline media and at higher elevated potentials. , These compounds enhance the oxidation and desorption of intermediate reaction products derived from the d -glucose electro-oxidation and their subsequent release from neighboring Pt active sites through the bifunctional or Langmuir–Hinshelwood mechanism. , The second contribution could be ascribed to the ligand effect. i.e., the variation in the electronic density of Pt due to the alloy formation with Ni, which may affect the adsorption of d -glucose molecules and the subsequent electro-oxidation process. , The third contribution involves the blockage of certain Pt sites by Ni atoms, favoring certain reaction pathways without reducing the electrocatalytic activity (ensemble effect) …”

Section: Resultsmentioning

confidence: 99%

Boosting the Electrolysis of Monosaccharide-Based Streams in an Anion-Exchange Membrane Cell

Serrano-Jiménez,

de la Osa,

Sánchez

et al. 2024

Energy Fuels

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A systematic study on the electrochemical reforming of monosaccharides (fructose, glucose, and xylose) using Ptbased anodic electrocatalysts is here presented for the first time to completely optimize the anodic catalyst and electrolyzer operating conditions. First, the electro-oxidation of each molecule was studied using a monometallic (Pt) and two bimetallic (PtNi and PtCo) anodic electrocatalysts supported on graphene nanoplatelets (GNPs). Tests in a three-electrode cell showed superior electrochemical activity and durability of PtNi/GNPs, especially at potentials higher than 1.2 V vs RHE, with the highest electrocatalytic activity in D-xylose electro-oxidation. Then, monometallic (Pt and Ni) and bimetallic electrocatalysts with different Pt:Ni mass ratios (1:1 and 2:1) were studied for D-xylose electro-oxidation, with the 2:1 mass ratio presenting the best results. This electrocatalyst was selected as the most suitable for scaleup to an anion-exchange membrane electrolyzer, where the optimal operating potential was determined. Additionally, stable operating conditions of the electrolyzer were achieved by cyclic H 2 production and cathodic regeneration polarization steps. This led to suitable and reproducible H 2 production rates throughout the production cycles for renewable hydrogen production from biomass-derived streams.

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Section: Resultsmentioning

confidence: 99%

Boosting the Electrolysis of Monosaccharide-Based Streams in an Anion-Exchange Membrane Cell

Serrano-Jiménez,

de la Osa,

Sánchez

et al. 2024

Energy Fuels

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“…16 Rh/C, Ni(OH) 2 /C, and Rhx{Ni(OH) 2 }y/C nanocomposite electrocatalysts were prepared by Xavier et al and applied in hydrogen production electrolyzers. 17 The electrochemical results showed that Rh 0.3 {Ni(OH) 2 } 0.7 /C present an overpotential of only 60 mV lower than the thermodynamic potential of the OER. Liquid chromatographic analysis of the products generated after 1 h electrolysis demonstrated that at 1.50 V vs RHE, the main reaction products were glyceraldehyde, glycerate, tartronate, and glycolate on the Rhx{Ni(OH) 2 }y/C.…”

Section: Introductionmentioning

confidence: 94%

“…Liquid chromatographic analysis of the products generated after 1 h electrolysis demonstrated that at 1.50 V vs RHE, the main reaction products were glyceraldehyde, glycerate, tartronate, and glycolate on the Rhx{Ni(OH) 2 }y/C. 17 Yu et al reported that 1.37 V is required to provide a current density of 100 mA cm −2 and to produce formate at the anode in a GEOR||HER. 18 All of these works reported noble metal-based and complex materials at the anode (or cathode), and all are based on nanoparticles.…”

Section: Introductionmentioning

confidence: 99%

“…Additionally, the constructed Pd-NCs/NiOuNPs||Pd-NCs/NiO-uNPs glycerol electrolyzer required 1.62 V to reach 10 mA·cm –2 of current density, lower than that of traditional water electrolysis (1.69 V) . Rh/C, Ni(OH) 2 /C, and Rhx{Ni(OH) 2 }y/C nanocomposite electrocatalysts were prepared by Xavier et al and applied in hydrogen production electrolyzers . The electrochemical results showed that Rh 0.3 {Ni(OH) 2 } 0.7 /C present an overpotential of only 60 mV lower than the thermodynamic potential of the OER.…”

Section: Introductionmentioning

confidence: 99%

“…The electrochemical results showed that Rh 0.3 {Ni(OH) 2 } 0.7 /C present an overpotential of only 60 mV lower than the thermodynamic potential of the OER. Liquid chromatographic analysis of the products generated after 1 h electrolysis demonstrated that at 1.50 V vs RHE, the main reaction products were glyceraldehyde, glycerate, tartronate, and glycolate on the Rhx{Ni(OH) 2 }y/C . Yu et al reported that 1.37 V is required to provide a current density of 100 mA cm –2 and to produce formate at the anode in a GEOR||HER .…”

Section: Introductionmentioning

confidence: 99%

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Glycerol Electrolyzer with Graphite Anode and Cathode Produces Carbonyl Compounds and Hydrogen: Background Electrocatalysis of a “Nonparticipating” Current Collector

Yonamine,

Zanata,

de Souza

et al. 2024

ACS Appl. Mater. Interfaces

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This study unveils a novel role of bare graphite as a catalyst in glycerol electrooxidation and hydrogen evolution reactions, challenging the prevailing notion that current collectors employed in electrolyzers are inert. Half-cell experiments elucidate the feasibility of glycerol oxidation and hydrogen production on bulk graphite electrodes at potentials exceeding 1.7 V. The investigation of varying glycerol concentrations (0.05 to 1.5 mol L −1 ) highlights a concentration-dependent competition between glycerol electrooxidation and oxygen evolution reactions. Employing an H-type glycerol electrolyzer, polarization curves reveal significant activation polarization attributed to the low electroactivity of the anode. Glycerol electrolysis at different concentrations yields diverse product mixtures, including formate, glycolate, glycerate, and lactate at the anode, with concurrent hydrogen generation at the cathode. The anolyte composition changes with glycerol concentration, resulting in less-oxidized compounds at higher concentrations and more oxidized compounds at lower concentrations. The cell voltage also influences the product formation selectivity, with an increased voltage favoring more oxidized compounds. The glycerol concentration also affects hydrogen production, with lower concentrations yielding higher hydrogen amounts, peaking at 3.5 V for 0.05 mol L −1 . This model quantitatively illustrates graphite's contribution to current and product generation in glycerol electrolyzers, emphasizing the significance of background current and products originating from current collectors if in contact with the reactants. These results have an impact on the efficiency of the electrolyzer and raise questions regarding possible extra non-noble "nonparticipating" current collectors that could affect overall performance. This research expands our understanding of electrocatalysis on graphite surfaces with potential applications in optimizing electrolyzer configurations for enhanced efficiency and product selectivity.

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3D Bimetallic Platinum‐Nickel Electrodes for Electro‐Oxidation of Glycerol at Ambient Conditions

Angizi,

Nankali,

Foroozan

et al. 2024

Adv Funct Materials

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Partial electro‐oxidation using renewable electricity offers a sustainable route for valorizing glycerol, a major by‐product of biofuel production. This study introduces a bimetallic electrode with nanostructured platinum dendrites on nickel foam (Pt/NiF), achieving a peak geometric current density of 235 mA cm−2 and a Pt‐mass normalized current density of 3.71 for glycerol electro‐oxidation at 0.92 V versus a reversible hydrogen electrode (RHE) in 3 m KOH electrolyte containing 1 m glycerol, outperforming most previously reported Pt‐containing catalysts. The Pt/NiF electrode demonstrates over 92% cumulative selectivity toward C3 products, with 64% selectivity for lactic acid at 0.65 V versus RHE over 5 h of testing. This research also highlights the role of chemical oxidation pathways (isomerization and rearrangements) in converting glycerol to lactic acid. After 5 h at 0.65 V versus RHE, the Pt/NiF electrode maintains 35% of its initial current density, plateauing at 12.2 mA cm−2 (0.15 ), with performance loss likely due to surface poisoning by carbon‐based reaction intermediates/byproducts or passivating platinum (hydr)oxide species. These findings pave the way for developing low‐platinum group metal catalysts with high glycerol oxidation affinity and highlight the importance of considering chemical transformations during catalyst evaluation and reactor design.

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Replacing oxygen evolution reaction by glycerol electrooxidation on Rh modified Ni(OH)2/C for energy-efficient hydrogen production

Cited by 13 publications

References 48 publications

Boosting the Electrolysis of Monosaccharide-Based Streams in an Anion-Exchange Membrane Cell

Boosting the Electrolysis of Monosaccharide-Based Streams in an Anion-Exchange Membrane Cell

Glycerol Electrolyzer with Graphite Anode and Cathode Produces Carbonyl Compounds and Hydrogen: Background Electrocatalysis of a “Nonparticipating” Current Collector

3D Bimetallic Platinum‐Nickel Electrodes for Electro‐Oxidation of Glycerol at Ambient Conditions

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