Electrooxidation of Anhydrous Glycerol: Kinetics and Selectivity DOI Creative Commons
Laela Ezra, Alasdair I. McKay, Matthias Drieß

et al.

ChemElectroChem, Journal Year: 2025, Volume and Issue: unknown

Published: April 8, 2025

As a by‐product of biofuel production, glycerol needs to find its use in various applications, for example, as substrate electrosynthesis more valuable chemicals. The oxidation reaction (GOR) aqueous media is technologically feasible but produces products with hard‐to‐control selectivity. Less explored the electrooxidation anhydrous glycerol, which theoretically limits possible aldehydes/ketones, including high‐cost glyceraldehyde. Herein, GOR gold electrodes investigated using and acetonitrile solvents without base, TEMPO (2,2,6,6‐tetramethylpiperidine 1‐oxyl) redox mediator, copper(I)‐bipyridyl catalyst added into lithium bis(trifluoromethanesulfonyl)imide electrolyte solutions. Both redox‐mediated heterogeneous are slow when used solvent even at 90 °C, particular probed by Fourier‐transformed alternating current voltammetry. Redox‐mediated glyceraldehyde achieved yield rate 6 ± 3 nmol s −1 cm −2 , essentially stops after ≈1 h electrolysis. Heterogeneous catalytic stable requires significantly positive potentials mix products. While demonstrating possibility selective electrooxidation, our results highlight need improvements mediator designs.

Language: Английский

pH‐Universal Electrocatalytic CO2 Reduction with Ampere‐Level Current Density on Doping‐Engineered Bismuth Sulfide DOI

Zinan Jiang,

Shan Ren, Xi Cao

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(32)

Published: May 27, 2024

Abstract The practical application of the electrocatalytic CO 2 reduction reaction (CO RR) to form formic acid fuel is hindered by limited activation molecules and lack universal feasibility across different pH levels. Herein, we report a doping‐engineered bismuth sulfide pre‐catalyst (BiS‐1) that S partially retained after electrochemical reconstruction into metallic Bi for RR formate/formic with ultrahigh performance wide range. best BiS‐1 maintains Faraday efficiency (FE) ~95 % at 2000 mA cm −2 in flow cell under neutral alkaline solutions. Furthermore, catalyst shows unprecedentedly high FE (~95 %) current densities from 100 1300 acidic Notably, density can reach 700 while maintaining above 90 membrane electrode assembly electrolyzer operate stably 150 h 200 . In situ spectra functional theory calculations reveals doping modulates electronic structure effectively promotes formation HCOO* intermediate generation. This work develops efficient stable electrocatalysts sustainable production.

Language: Английский

Citations

19
Efficient Electrocatalytic Oxidation of Glycerol to Formate Coupled with Nitrate Reduction over Cu‐Doped NiCo Alloy Supported on Nickel Foam DOI
Chen‐Yang Li, Hao Li, Bo Zhang

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(46)

Published: Aug. 12, 2024

Abstract Electrooxidation of biomass‐derived glycerol which is regarded as a main byproduct industrial biodiesel production, an innovative strategy to produce value‐added chemicals, but currently showcases slow kinetics, limited Faraday efficiency, and unclear catalytic mechanism. Herein, we report high‐efficiency electrooxidation into formate via Cu doped NiCo alloy catalyst supported on nickel foam (Cu−NiCo/NF) in coupled system paired with nitrate reduction. The designed Cu−NiCo/NF delivers only 1.23 V vs . RHE at 10 mA cm −2 , record efficiency 93.8 %. superior performance ascribed the rapid generation Ni III −OOH Co species favorable coupling surface *O reactive intermediates. Using bifunctional catalyst, synchronously produces NH 3 formate, showing 290 mV lower than hydrogen evolution reaction, together excellent long‐term stability for up 144 h. This work lays out new guidelines reliable strategies from design electrochemical refinery.

Language: Английский

Citations

18
Advancements in catalysts for glycerol oxidation via photo-/electrocatalysis: a comprehensive review of recent developments DOI
Mohit Kumar,

Bhagatram Meena,

Aimin Yu

et al.

Green Chemistry, Journal Year: 2023, Volume and Issue: 25(21), P. 8411 - 8443

Published: Jan. 1, 2023

Photoelectrocatalytic and electrocatalytic oxidation of glycerol to valuable products relies on robust, highly active photo-/electrocatalysts. This review emphasizes conversion significance recent advancements in its valorization.

Language: Английский

Citations

23
Strongly Coupled Heterostructured CoP/MoO2 as an Advanced Electrocatalyst for Urea-Assisted Water Electrolysis DOI
Zhiwei Liu,

Zhenjiang Lu,

Yali Cao

et al.

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(5), P. 2803 - 2813

Published: Jan. 20, 2024

Developing low-cost electrocatalysts with excellent activity and durability in urea-assisted water splitting is urgently needed order to achieve sustainable hydrogen production. Herein, we situ synthesized a robust coupled heterostructured electrocatalyst (CoP/MoO2) on nickel foam (NF) substrate explored its electrocatalytic performances the evolution reaction (HER), oxygen (OER), urea oxidation (UOR). The overpotential of CoP/MoO2/NF found be only 11 mV at 10 mA cm–2 during HER process, which significantly lower than that commercial Pt/C. Meanwhile, UOR catalytic performance indicates fast kinetics, along considerable low driving potential (1.26 V) compared OER (1.51 V). In ex techniques demonstrate these properties are mainly ascribed effective synergistic effect strong electronic interactions between single-component CoP MoO2, can tune states Co Mo, expose more active sites, enhance intrinsic activity, accelerate charge transfer. Moreover, when used electrochemical overall electrolysis, reach current density 1.46 1.32 V. This outperforms Pt/C||RuO2 numerous nonprecious metal maintains stable long-term electrolytic operation for 84 h. work provides promising pathway development efficient catalysts electrolysis

Language: Английский

Citations

14
An overview of pure hydrogen production via electrolysis and hydrolysis DOI
Siu Hua Chang, Mohd Fariz Rajuli

International Journal of Hydrogen Energy, Journal Year: 2024, Volume and Issue: 84, P. 521 - 538

Published: Aug. 22, 2024

Language: Английский

Citations

14
Efficient paired electrolysis of glycerol upgrading with hydrogen fuel over heterostructured Fe-Co2Mo3O8@Co electrocatalyst DOI
Guorong Zhou, Nan Zhang, Zhihui Huang

et al.

Chemical Engineering Journal, Journal Year: 2024, Volume and Issue: 503, P. 158619 - 158619

Published: Dec. 18, 2024

Language: Английский

Citations

13
Decoupled electrolysis for hydrogen production and hydrazine oxidation via high-capacity and stable pre-protonated vanadium hexacyanoferrate DOI Creative Commons
Fei Lv,

Jiazhe Wu,

Xuan Liu

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Feb. 13, 2024

Abstract Decoupled electrolysis for hydrogen production with the aid of a redox mediator enables two half-reactions operating at different rates, time, and spaces, which offers great flexibility in operation. Herein, pre-protonated vanadium hexacyanoferrate (p-VHCF) is synthesized. It high reversible specific capacity up to 128 mAh g −1 long cycling performance 6000 cycles retention about 100% current density 10 A due enhanced bonding network. By using this mediator, membrane-free water electrolytic cell built achieve decoupled oxygen production. More importantly, system hydrazine oxidation constructed, realizes not only separate generation but electricity through p-VHCF-N 2 H 4 liquid battery. Therefore, work flexible energy conversion storage driven by solar day-time output night-time.

Language: Английский

Citations

9
Design of Bi-functional mixed oxide electrodes for selective oxidative C–C cleavage of glycerol to formate and synchronized green hydrogen production DOI
Arindam Saha,

Vasantharadevi Murugiah,

Ravi Ranjan

et al.

Sustainable Energy & Fuels, Journal Year: 2024, Volume and Issue: 8(13), P. 2954 - 2968

Published: Jan. 1, 2024

NiCoMn oxide nanoneedles with a cactus-like morphology are shown as bifunctional electrocatalysts that selectively oxidize glycerol to HCOOH and concurrently produce H 2 .

Language: Английский

Citations

9
Electro-Refinery in Organics to Produce Energy Carriers: Co-Generation of Green Hydrogen and Carboxylic Acids by Glycerol Electrooxidation Using Dimensionally Stable Anode DOI Open Access

Letícia M. G. da Silva,

Letícia G. A. Costa, José Eudes L. Santos

et al.

Catalysts, Journal Year: 2025, Volume and Issue: 15(4), P. 333 - 333

Published: March 31, 2025

The urgency to decarbonize fuels has contributed a rise in biofuel production, which culminated significant increase the waste quantity of glycerol produced. Therefore, convert into high-value products, electrochemical oxidation (EO) is viable alternative for co-generation carboxylic acids, such as formic acid (FA) and green hydrogen (H2), are considered energy carriers. aim this study electroconversion FA by EO using divided cell, driven photovoltaic (PV) system, with dimensionally stable anode (DSA, Ti/TiO2-RuO2-IrO2) electrode an Ni-Fe stainless steel (SS) mesh cathode. To optimize experimental conditions, studies were carried out evaluating effects applied current density (j), electrolyte concentration, electrolysis time, cell configuration (undivided divided). According results, optimum conditions achieved at 90 mA cm−2, 0.1 mol L−1 Na2SO4 supporting electrolyte, 480 min electrolysis. In condition, 256.21 211.17 mg obtained undivided cells, respectively, while 6.77 L dry H2 was cell. process under also real sample, where organic acids like acetic co-produced simultaneously H2. Based on preliminary economic analysis, integrated-hybrid economically promising when it integrated renewable sources solar energy.

Language: Английский

Citations

1
Electrocatalytic Glycerol Conversion: A Low-Voltage Pathway to Efficient Carbon-Negative Green Hydrogen and Value-Added Chemical Production DOI
Inderjeet Chauhan, Himanshu Bajpai, Bishakha Ray

et al.

ACS Applied Materials & Interfaces, Journal Year: 2024, Volume and Issue: 16(20), P. 26130 - 26141

Published: May 8, 2024

Electrochemical glycerol oxidation reaction (GLYOR) could be a promising way to use the abundantly available for production of value-added chemicals and fuels. Completely avoiding oxygen evolution (OER) with GLYOR is an evolving strategy reduce overall cell potential generate fuels on both anode cathode. We demonstrate morphology-controlled palladium nanocrystals, afforded by colloidal chemistry, their established morphology-dependent performance. Although it known that controlling morphology electrocatalyst can modulate activity selectivity products, still relatively underexplored area many reactions, including GLYOR. Among nanocube (Pd-NC), truncated octahedron (Pd-TO), spherical polycrystalline (Pd-PC) morphologies, Pd-NC deposited Ni foam exhibits highest conversion (85%) along 42% glyceric acid at low applied 0.6 V (vs reversible hydrogen electrode (RHE)) in 0.1 M 1 KOH ambient temperature. Owing much favorable thermodynamics surface, assembled electrolyzer requires electricity input only ∼3.7 kWh/m3 H2 current density 100 mA/cm2, contrast requirement ≥5 alkaline/PEM electrolyzer. Sustainability has been successfully demonstrated 10 50 mA/cm2 up 120 h water simulated seawater.

Language: Английский

Citations

8