Selective oxidation of glycerol over supported noble metal catalysts

He, Zhiyan; Ning, Xiaomei; Yang, Guangxing; Wang, Hongjuan; Cao, Yonghai; Peng, Feng

doi:10.1016/j.cattod.2020.04.019

Cited by 47 publications

(33 citation statements)

References 110 publications

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“…The reaction is commonly described in the literature under basic conditions, mainly due to the fact that alkaline media accelerates the reaction, improves the selectivity to C3 products, and prevents deactivation [183]. Recent advances in the employment of noble metals as active phases, especially Au and Pt, are focused on selective oxidation base-free and room condition reactions [29,[184][185][186][187]. In this line, support properties may be key to achieving this objective through metal particle sintering prevention [188], as well as the establishment of metal synergies with superficial acid-base centers [189].…”

Section: Glycerol Selective Oxidationmentioning

confidence: 99%

Recent Advances in Glycerol Catalytic Valorization: A Review

et al. 2020

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Once a biorefinery is ready to operate, the main processed materials need to be completely evaluated in terms of many different factors, including disposal regulations, technological limitations of installation, the market, and other societal considerations. In biorefinery, glycerol is the main by-product, representing around 10% of biodiesel production. In the last few decades, the large-scale production of biodiesel and glycerol has promoted research on a wide range of strategies in an attempt to valorize this by-product, with its transformation into added value chemicals being the strategy that exhibits the most promising route. Among them, C3 compounds obtained from routes such as hydrogenation, oxidation, esterification, etc. represent an alternative to petroleum-based routes for chemicals such as acrolein, propanediols, or carboxylic acids of interest for the polymer industry. Another widely studied and developed strategy includes processes such as reforming or pyrolysis for energy, clean fuels, and materials such as activated carbon. This review covers recent advances in catalysts used in the most promising strategies considering both chemicals and energy or fuel obtention. Due to the large variety in biorefinery industries, several potential emergent valorization routes are briefly summarized.

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Section: Glycerol Selective Oxidationmentioning

confidence: 99%

Recent Advances in Glycerol Catalytic Valorization: A Review

et al. 2020

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“…Glycerol is a by-product of the biodiesel manufacturing process. Because the increase in biodiesel production caused glycerol oversupply, a selective oxidation technique is required to change glycerol into valuable compounds, including glyceric acid (GA), dihydroxyacetone (DHA), and hydroxypyruvic acid (HA) [1][2][3][4]. HA is an important intermediate in the pharmaceutical and chemical industries owing to its high functionality, that is, three different functional groups of hydroxyl, carbonyl, and carboxyl groups [5,6].…”

Section: Introductionmentioning

confidence: 99%

“…Based on previous studies [1][2][3][4], glycerol oxidation routes have been proposed, as shown in Figure 1. In the first step, the terminal and secondary OH groups in glycerol are oxidized to form glyceraldehyde (GLA) and DHA, respectively, where GLA is easily oxidized into a more chemically stable compound of GA.…”

Section: Introductionmentioning

confidence: 99%

“…In the first step, the terminal and secondary OH groups in glycerol are oxidized to form glyceraldehyde (GLA) and DHA, respectively, where GLA is easily oxidized into a more chemically stable compound of GA. The selectivities of GA and DHA were affected by the pH of the reaction solution and the nature of the catalysts [4]. In the base condition, glycerate salts were predominantly formed rather than DHA.…”

Section: Introductionmentioning

confidence: 99%

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Production of Hydroxypyruvic Acid by Glycerol Oxidation over Pt/CeO2-ZrO2-Bi2O3-PbO/SBA-16 Catalysts

et al. 2022

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Pt/CeO2-ZrO2-Bi2O3-PbO/SBA-16 (SBA-16: Santa Barbara Amorphous No. 16) catalysts were synthesized to produce hydroxypyruvic acid by glycerol oxidation. In the catalysts, the introduction of PbO into CeO2-ZrO2-Bi2O3 improved the oxygen release and storage abilities owing to the synergistic redox reaction of Pb2+/4+ and Ce3+/4+, which facilitated the oxidation ability of Pt. In addition, the oxidation of the secondary OH group in glycerol might be accelerated by the geometric effects of glycerol, Pt, and Bi3+ or Pb2+/4+. Furthermore, the moderate reaction conditions such as room temperature and open-air atmosphere enabled the suppression of further oxidation of hydroxypyruvic acid. The highest catalytic activity was obtained for 7 wt% Pt/16 wt% Ce0.60Zr0.15Bi0.20Pb0.05O2−δ/SBA-16, which provided a hydroxypyruvic acid yield maximum of 24.6%, after the reaction for 6 h at 30 °C in atmospheric air.

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“…Although the two terminal (primary) hydroxyl groups within glycerol are more reactive to produce glyceraldehyde (GLYD) and glyceric acid (GLYA), the secondary hydroxyl is more preferred to be oxidized to produce dihydroxyacetone (DHA) as shown in Figure 1(A), serving as important roles in cosmetics and fine chemical industries 9,10 . Along this line, extensive efforts have been devoted to the catalyst exploration for this selective oxidation reaction, including noble metals (e.g., Ru, Pd, Pt, and Au) and non‐noble metals (e.g., Cr, Mn, Co, Ni, and Cu), and a general consensus is Pt exhibiting relatively higher catalytic activity 11–15 . Despite significant progress made to increase Pt utilization efficiency and lower Pt usage, the structural design and development of high‐performance Pt catalyst to simultaneously achieve high activity and selectivity still remain challenging yet desirable to obtain the targeted DHA product.…”

Section: Introductionmentioning

confidence: 99%

Kinetics decoupling activity and selectivity of Pt nanocatalyst for enhanced glycerol oxidation performance

et al. 2021

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Herein, we demonstrate a kinetics and a mechanistic strategy to disentangle the origins of the significantly improved activity and selectivity of Pt‐catalyzed glycerol oxidation. The unchanged reactant reaction orders and activation energies suggest the same kinetics despite variable Pt particle sizes, based on which a Michaelis–Menten kinetics treatment is conducted to individually quantify the number and activity of Pt active site. Together with multiple characterization results, the volcano‐shaped activity is mainly arising from the quantity change of Pt active site. Moreover, the atomic structure of bimetallic Pt─Sb catalyst is well elucidated by the formation of Pt─SbO interface along with partial Sb incorporation into Pt lattice, chelating with glycerol to poison Pt active sites for primary hydroxyl activation while creating interfacial site for second hydroxyl activation, further evidenced by kinetics shift. The kinetics strategy could be extended to other metal catalysts with simultaneously high activity and selectivity.

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Selective oxidation of glycerol over supported noble metal catalysts

Cited by 47 publications

References 110 publications

Recent Advances in Glycerol Catalytic Valorization: A Review

Recent Advances in Glycerol Catalytic Valorization: A Review

Production of Hydroxypyruvic Acid by Glycerol Oxidation over Pt/CeO2-ZrO2-Bi2O3-PbO/SBA-16 Catalysts

Kinetics decoupling activity and selectivity of Pt nanocatalyst for enhanced glycerol oxidation performance

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