Glycerol electro-oxidation to dihydroxyacetone on phosphorous-doped Pd/CNT nanoparticles in alkaline medium

Ahmad, Muhammad Sheraz; Singh, Sharanjit; Cheng, Chin Kui; Ong, Huei Ruey; Abdullah, Huda; Khan, Maksudur R.; Wongsakulphasatch, Suwimol

doi:10.1016/j.catcom.2020.105964

Cited by 27 publications

(11 citation statements)

References 33 publications

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“…In the GOR, lactic acid (structure 1m ) can be produced with high selectivity and FE (73% and >86%, respectively) on AuPt alloys electrodes, while dihydroxyacetone (DHA, also called 1,3-dihydroxypropan-2-one, structure 1h ) can be obtained with both selectivity and FE close to 100% on Bi-modified Pt electrodes . Noteworthy activity toward this product has also been obtained on PtSb/C catalysts (yield and glycerol conversion of 61.4% and 90.3%, respectively), PtAg skeletons (selectivity of 82.6%), and P-doped Pd/carbon nanotubes (selectivity of 90.8%) . Indirect electrolysis of glycerol mediated by TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl) also showed selectivity toward DHA but with lower yield (30%). , DHA is the most valuable product of the GOR, costing $150/kg (crude and refined glycerol cost $0.11 and $0.66/kg, respectively) .…”

Section: Demonstrated Electrochemical Routes For Conversion Of Interm...mentioning

confidence: 99%

“…106 Noteworthy activity toward this product has also been obtained on PtSb/C catalysts (yield and glycerol conversion of 61.4% and 90.3%, respectively), 111 PtAg skeletons (selectivity of 82.6%), 114 and P-doped Pd/carbon nanotubes (selectivity of 90.8%). 119 Indirect electrolysis of glycerol mediated by TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl) also showed selectivity toward DHA but with lower yield (30%). 120,121 DHA is the most valuable product of the GOR, costing $150/kg (crude and refined glycerol cost $0.11 and $0.66/kg, respectively).…”

Section: Demonstrated Electrochemical Routes For Conversion Of Interm...mentioning

confidence: 99%

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Electrochemical Routes for the Valorization of Biomass-Derived Feedstocks: From Chemistry to Application

et al. 2021

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The drive to reduce consumption of fossil resources, coupled with expanding capacity for renewable electricity, invites the exploration of new routes to utilize this energy for the sustainable production of fuels, chemicals, and materials. Biomass represents a possible source of platform precursors for such commodities due to its inherent ability to fix CO 2 in the form of multi-carbon organic molecules. Electrochemical methods for the valorization of biomass are thus intriguing, but there is a need to objectively evaluate this field and define the opportunity space by identifying pathways suited to electrochemistry. In this contribution we offer a comprehensive, critical review of recent advances in lowtemperature (liquid phase), electrochemical reduction and oxidation of biomass-derived intermediates (polyols, furans, carboxylic acids, amino acids, and lignin), with emphasis on identifying the state-of-the-art for each documented reaction. Progress in computational modeling is also reviewed. We further suggest a number of possible reactions that have not yet been explored but which are expected to proceed based on established routes to transform specific functional groups. We conclude with a critical discussion of technological challenges for scale-up, fundamental research needs, process intensification opportunities (e.g., by pairing compatible oxidations and reductions), and new benchmarking standards that will be necessary to accelerate progress toward application in this still-nascent field.

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Section: Demonstrated Electrochemical Routes For Conversion Of Interm...mentioning

confidence: 99%

Section: Demonstrated Electrochemical Routes For Conversion Of Interm...mentioning

confidence: 99%

Electrochemical Routes for the Valorization of Biomass-Derived Feedstocks: From Chemistry to Application

et al. 2021

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“…More recently, the phosphorous‐doped Pd nanoparticles supported on carbon nanotubes (P‐Pd/CNT) attained a large electrochemical surface area of 392.22 m 2 g Pd −1 , a high current density of 26 mA cm −2 , and a high selectivity of 90.82% to DHA production in 0.5 m KOH solution with the presence of 0.5 m glycerol, far beyond those of bare Pd/CNT. [ 49 ] Such excellent GOR performance was believed to derive from the interaction between P and Pd/CNT that facilitated reduction of Pd 2+ to metallic Pd, inhibited generation of carbonaceous intermediates, and increased the OH concentration on Pd surface.…”

Section: Electrocatalystsmentioning

confidence: 99%

Recent Progress in Electrocatalytic Glycerol Oxidation

et al. 2020

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Glycerol, as the major by‐product of biodiesel, can be oxidized into diverse value‐added chemical products via either traditional chemical methods or electrochemical routes. Electrocatalytic glycerol oxidation reaction (GOR) driven by renewable‐derived electricity (e.g., wind and solar) is a promising pathway for fine chemicals production. In an electrochemical cell, GOR can be coupled with various cathodic reactions, including hydrogen evolution reaction (HER), CO2 reduction reaction (CO2RR), and oxygen reduction reaction (ORR); in this manner, different benefits of either energy effectiveness or additional value‐added products can be obtained depending on the cathode reduction reaction selected. Comprehensively understanding of electrocatalytic GOR and the associated processes is of great significance to promote its industrial application. Herein, recent progress of GOR is focused on. The background of biomass‐derived glycerol valorization to energy and value‐added chemicals as well as the electrochemical conversion techniques via GOR is introduced. Then, the electrocatalytic reaction pathways, the potential application of GOR, and the measurement method for products are also discussed and summarized. Special emphasis is put on the design and the development of high‐selectivity and high‐activity electrocatalysts for GOR. Finally, the challenges and the future prospects in the fields of GOR are highlighted.

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“…As byproducts of the biodiesel and coal chemical industry, low-value polyols (especially glycerol) have been oversupplied to the market. , Polyol workup for the production of value-added chemicals has therefore attracted much attention. − The triple hydroxyl functional groups in glycerol render it a potential platform chemical for the synthesis of a variety of valuable chemicals, including glycolic acid, dihydroxyacetone, hydroxyacetone, and acetone. − Several catalytic conversion pathways of glycerol have been investigated, including oxidation, , hydrogenolysis, dehydration, , and dehydrogenation. , However, these processes in general require considerable energy input and expensive catalysts and are operated under elevated pressure and temperature.…”

Section: Introductionmentioning

confidence: 99%

Effect of Pd and Au on Hydrogen Abstraction and C–C Cleavage in Photoconversion of Glycerol: Beyond Charge Separation

Lei

Zhang

et al. 2020

J. Phys. Chem. C

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Photocatalytic conversion of polyols to value-added products is of great interest for the utilization of biomass as a chemical feedstock. Current research focuses on boosting the reaction rate and selectivity by employing metal nanoparticles (NPs) as charge separators and cocatalysts. However, the promotional role of metal NPs in such photocatalytic processes still remains unclear because of the lack of mechanistic understanding. Here, we have explored the role of supported Pd and Au NPs on TiO 2 in photocatalytic glycerol conversion under water-free, deaerated conditions by in situ spectroscopic methods. While the presence of Au NPs only results in partial conversion of glycerol at a low rate, Pd decoration promotes glycerol oxidation to a much higher conversion. In situ mass and vibrational spectrometry reveals that Pd/TiO 2 exhibits faster cleavage of O−H and C−H bonds in both glycerol and the derived intermediates as compared to Au/TiO 2 , thus leading to a higher glycerol conversion accompanied by the formation of additional molecular hydrogen. X-ray photoelectron spectroscopy suggests that the preferential adsorption of glycerol on the surface of Pd via hydroxyl groups results in an enhanced interfacial charge transfer, thus yielding a better photocatalytic activity.

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Glycerol electro-oxidation to dihydroxyacetone on phosphorous-doped Pd/CNT nanoparticles in alkaline medium

Cited by 27 publications

References 33 publications

Electrochemical Routes for the Valorization of Biomass-Derived Feedstocks: From Chemistry to Application

Electrochemical Routes for the Valorization of Biomass-Derived Feedstocks: From Chemistry to Application

Recent Progress in Electrocatalytic Glycerol Oxidation

Effect of Pd and Au on Hydrogen Abstraction and C–C Cleavage in Photoconversion of Glycerol: Beyond Charge Separation

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