Reaction pathway investigation using in situ Fourier transform infrared technique over Pt/CuO and Pt/TiO2 for selective glycerol oxidation

Wu, Guandong; Liu, Yanan; He, Yufei; Feng, Junting; Li, Dianqing

doi:10.1016/j.apcatb.2021.120061

Cited by 37 publications

(28 citation statements)

References 45 publications

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“…Figure 5a shows that the peak of the intermolecular hydrogen bonds of glycerol in the 1660-1640 cm −1 gradually disappears with the increase of temperature, and the peak of C=O bond is dominant at high temperature (≥80 o C), proving that glycerol converts into carboxylic acid products. 55 Meanwhile, the νCO region in Figure 5b shows that the characteristic peaks of α interaction in the 1125-1075 cm −1 (belonging to alkoxy bond from primary hydroxyl and active sites) and γ interaction in the 1075-1000 cm −1 (belonging to primary hydroxyl) shift to the high wavelength with the increase of temperature, indicating the activation of primary hydroxyl group of glycerol. 55 In contrast, the position of the characteristic peak of β interaction in the 1200-1125 cm −1 (belonging to the activation of secondary hydroxyl) remains unchanged.…”

Section: Resultsmentioning

confidence: 94%

“…55 Meanwhile, the νCO region in Figure 5b shows that the characteristic peaks of α interaction in the 1125-1075 cm −1 (belonging to alkoxy bond from primary hydroxyl and active sites) and γ interaction in the 1075-1000 cm −1 (belonging to primary hydroxyl) shift to the high wavelength with the increase of temperature, indicating the activation of primary hydroxyl group of glycerol. 55 In contrast, the position of the characteristic peak of β interaction in the 1200-1125 cm −1 (belonging to the activation of secondary hydroxyl) remains unchanged. This further con rms that glycerol is mainly oxidized to glyceric acid via the activation of primary hydroxyl rather than secondary hydroxyl on Pt 1 /HAP (Figure 5c), which is consistent with the results of DFT calculation.…”

Section: Resultsmentioning

confidence: 94%

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Switchable Structure Promoted Leaching Free Atomically Dispersed Pt Catalyst for Low Carbon Biomass Polyol Oxidation

Hao

Zhao

Zhou

et al. 2021

Preprint

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Achieving efficient catalytic conversion over heterogeneous catalyst with excellent resistance against leaching is still a grand challenge for sustainable chemical synthesis in aqueous solution. Herein, we devised a leaching free atomically dispersed Pt1/hydroxyapatite (HAP) catalyst with unique switchable structure via a simple and green in-situ anchoring strategy. Gratifyingly, this robust Pt1/HAP catalyst exhibits remarkable catalytic selectivity and catalyst stability for the selective oxidation of C2-C4 bio-polyols (e.g., ethylene glycol, propanediol, glycerol and butanediol) to corresponding primary hydroxy acids. X-ray absorption spectroscopy, in-situ Fourier Transform infrared spectroscopy, density functional theory calculation and kinetics study elucidated that the switchable Pt-(O-P) linkages with strong electronic-withdrawing function of PO43− (Pt1-OPO43− active site) not only realize the activation of C-H bond, but also destabilize the transition state from adsorbed hydroxy acids toward the C-C cleavage, resulting in the sharply increased selectivity of hydroxy acids. Moreover, the strong PO43−-coordination effect, originating from the enhanced interaction between positively charged Pt1 and negatively charged OPO43−, provides electrostatic stabilization for the atomically dispersed Pt, ensuring the highly efficient catalysis of Pt1/HAP for over 160 hours without metal leaching. This finding opens up new opportunities for efficient upgrading of bio-polyols over atomically dispersed catalysts.

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Section: Resultsmentioning

confidence: 94%

Section: Resultsmentioning

confidence: 94%

Switchable Structure Promoted Leaching Free Atomically Dispersed Pt Catalyst for Low Carbon Biomass Polyol Oxidation

Hao

Zhao

Zhou

et al. 2021

Preprint

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“…Meanwhile, the metal oxides can inhibit agglomeration of the supported metallic nanoparticles because of the strong metal-support interaction (SMSI). [19][20][21][22] Li et al found that the metal oxides took part in the GLY oxidation to enhance the catalytic activity and tune the selectivity. [20] It showed that Pt/ CuO catalyst gave rise to DHA product, while Pt/TiO 2 produced GLYA product, proposing that the Pt-O surface site was conducive to activate the secondary hydroxyl in the GLY molecular for Pt/ CuO and the Pt-Ti surface site was responsible for the activation of primary hydroxyl group to produce GLYA.…”

Section: Introductionmentioning

confidence: 99%

“…[19][20][21][22] Li et al found that the metal oxides took part in the GLY oxidation to enhance the catalytic activity and tune the selectivity. [20] It showed that Pt/ CuO catalyst gave rise to DHA product, while Pt/TiO 2 produced GLYA product, proposing that the Pt-O surface site was conducive to activate the secondary hydroxyl in the GLY molecular for Pt/ CuO and the Pt-Ti surface site was responsible for the activation of primary hydroxyl group to produce GLYA. Besides, carbon nanotube (CNT), as a superior support material is also utilized in the GLY oxidation because it can boost the electron transfer and inhibit the agglomeration and sintering.…”

Section: Introductionmentioning

confidence: 99%

Chemoselective Oxidation of Glycerol over Platinum‐Based Catalysts: Toward the Role of Oxide Promoter

Yang

Song

et al. 2022

ChemCatChem

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The metal oxide promoters remarkably enhance the catalytic activity of supported Pt catalysts in the glycerol oxidation toward glyceric acid, whereas the primary factor that metal oxide promotes the reaction, as well as the kinetics relevant step remain indistinct. Herein, manganese dioxide (MnO2) is chosen as a model to uncover the role of promoter in the glycerol oxidation over Pt‐based catalyst in alkali‐free solution. The results prove that the superior catalytic performance is mainly attributed to the increased synergistic interaction between Pt particles and the metal oxides to boost the activation of oxygen (not glycerol), while the increased dispersion shows slight effect. Furthermore, the detailed kinetic studies reveal that MnO2 is prone to accelerate the awkward step of glyceraldehyde to glyceric acid, and the lattice oxygen of MnO2 also involves in this particular step.

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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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Reaction pathway investigation using in situ Fourier transform infrared technique over Pt/CuO and Pt/TiO2 for selective glycerol oxidation

Cited by 37 publications

References 45 publications

Switchable Structure Promoted Leaching Free Atomically Dispersed Pt Catalyst for Low Carbon Biomass Polyol Oxidation

Switchable Structure Promoted Leaching Free Atomically Dispersed Pt Catalyst for Low Carbon Biomass Polyol Oxidation

Chemoselective Oxidation of Glycerol over Platinum‐Based Catalysts: Toward the Role of Oxide Promoter

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

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