Understanding size-dependent hydrogenation of dimethyl oxalate to methyl glycolate over Ag catalysts

Dong, Guilin; Luo, Zuwei; Cao, Yueqiang; Zheng, Sainan; Zhou, Jinghong; Li, Wei; Zhou, Xinggui

doi:10.1016/j.jcat.2021.07.028

Cited by 29 publications

(24 citation statements)

References 62 publications

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“…If one type of surface site dominates the reaction, the activity of such a site should be a constant, and thus the normalized TOF based on the number of such a site should be insensitive to the particle size. ,,, To further confirm the identification of dominant active sites for the reaction, the reaction rates for DADNP conversion over differently sized Pd catalysts were normalized according to the number of each type of surface site, which gives rise to the corresponding TOF for DADNP conversion, that is, TOF corner , TOF edge , TOF (100) , and TOF (111) . The obtained values of these four kinds of TOFs were further normalized by the corresponding highest TOF to yield the normalized TOFs.…”

Section: Resultsmentioning

confidence: 99%

“…Catalysis is well known as a kinetics process, and understanding the kinetics behaviors is of significance for tailoring and designing catalysts, , especially at the level of active sites. For heterogeneous hydrogenations, − the catalytic performances and kinetics are associated with the sizes of supported metal nanoparticles, which is also known as the so-called structure sensitivity. Selective hydrogenation of the aromatic nitro group over supported metal catalysts, as exemplified by Rh-catalyzed hydrogenation of 3-nitroacetophenone and Au-catalyzed one of 4-nitrophenol, was elucidated to be strongly dependent on the metal particle sizes.…”

Section: Introductionmentioning

confidence: 99%

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Size Dependence of Pd-Catalyzed Hydrogenation of 2,6-Diamino-3,5-dinitropyridine

Chen

Cao

et al. 2022

Ind. Eng. Chem. Res.

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An in-depth understanding of the effects of metal particle sizes on reactions is crucial for tailoring and designing catalysts. Herein, the Pd/CNT catalysts with different Pd particle sizes were prepared and employed to explore the size effects on the Pdcatalyzed hydrogenation of 2,6-diamino-3,5-dinitropyridine (DADNP). The apparent turnover frequencies for DADNP conversion and target 2,3,5,6-tetraaminopyridine (TAP) formation are found to exhibit strong dependence on the Pd particle sizes, indicating that the hydrogenation of DADNP to TAP is typically structure-sensitive. The size-insensitive activation energies extracted from the kinetics studies for DADNP conversion on ≥2.6 nmsized Pd catalysts with similar electronic properties suggest the presence of only one type of active site mainly dominating the reaction. Further combining model calculations based on the cuboctahedron shape for Pd nanoparticles characterized by electron microscopy, the (111) sites are demonstrated as the dominant active sites for DADNP conversion on the ≥2.6 nm-sized Pd catalysts. However, for the Pd catalyst size <2.6 nm, the reaction is shown to be mainly dominated by the Pd electronic properties.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Size Dependence of Pd-Catalyzed Hydrogenation of 2,6-Diamino-3,5-dinitropyridine

Chen

Cao

et al. 2022

Ind. Eng. Chem. Res.

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“…As it has similar chemical properties to alcohol and ester, MG can undergo various reactions such as carbonylation, hydrolyzation, and oxidation [ 4 , 5 ]. Many traditional synthetic technologies, such as the carboxylation of formaldehyde and condensation of methyl formate with formaldehyde [ 2 , 6 , 7 ], have been applied for the synthesis of MG. However, disadvantages such as environmental pollution, harsh production process, and low stability of catalyst are obvious [ 2 , 6 , 7 ].…”

Section: Introductionmentioning

confidence: 99%

“…Many traditional synthetic technologies, such as the carboxylation of formaldehyde and condensation of methyl formate with formaldehyde [ 2 , 6 , 7 ], have been applied for the synthesis of MG. However, disadvantages such as environmental pollution, harsh production process, and low stability of catalyst are obvious [ 2 , 6 , 7 ]. Thus, the development of a green synthetic method with high efficiency is warranted.…”

Section: Introductionmentioning

confidence: 99%

“…To make sure that the hydrogenation of DMO stops at the formation of MG, catalysts with relatively weak hydrogenolysis ability should be used. Ag-based catalysts such as Ag/MCM-41 [ 12 ], Ag/SBA-15 [ 13 ], Ag/CNT [ 14 ], Ag/KCC-1 [ 15 , 16 ], Ag/SiO 2 [ 17 ], Ag/AC-N [ 18 ], and Ag/AS [ 7 ] have been reported for that purpose. However, the catalytic activity and stability should be improved [ 19 , 20 ] in order to satisfy industrial demands and practical application.…”

Section: Introductionmentioning

confidence: 99%

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Ni-Modified Ag/SiO2 Catalysts for Selective Hydrogenation of Dimethyl Oxalate to Methyl Glycolate

et al. 2022

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Ni-modified Ag/SiO2 catalysts containing 0~3 wt.% Ni were obtained by impregnating Ni species onto Ag/SiO2 followed by calcination and reduction. The catalysts’ performance in the hydrogenation of dimethyl oxalate (DMO) to methyl glycolate (MG) was tested. Ag-0.5%Ni/SiO2 showed the highest catalytic activity among these catalysts and exhibited excellent catalytic stability. The effects of the Ni content on the structure and surface chemical states of catalysts were investigated by XRF, N2-sorption, XRD, TEM, EDX-mapping, FT-IR, H2-TPR, UV–vis, and XPS. The better catalytic activity and stability of Ni-modified Ag/SiO2 (versus Ag/SiO2) are ascribed to the improved dispersion of active Ag species as well as the higher resistance to the growth of Ag particles due to the presence of Ni species.

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Kinetics‐assisted identification and regulation of active sites for Pd‐catalyzed propyne selective hydrogenation

Yan

Cao

et al. 2022

AIChE Journal

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Identification and regulation of active sites are significant for guiding the design and optimization of hydrogenation catalysts toward the target product but remain a great challenge. Herein, we demonstrate a kinetics‐assisted identification method combined with theoretical calculations for identifying and further regulating the dominant active sites of Pd catalysts for propyne hydrogenation. Kinetics analysis and model calculations based on the cuboctahedron shape of Pd nanoparticles in the catalysts indicate the Pd(111) sites as the dominant active sites for the propyne conversion and propylene formation while the Pd(100) sites as those for the propane formation, which are further rationalized by theoretical calculations. Moreover, the Pd catalyst with electron‐rich properties exhibits relatively higher activity and selectivity, guided by which the SiO2 support with abundant electron‐donating hydroxyl groups is employed to increase the Pd electron density. Such electronic regulation for the Pd catalyst clearly enhances the selective hydrogenation of propyne.

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Understanding size-dependent hydrogenation of dimethyl oxalate to methyl glycolate over Ag catalysts

Cited by 29 publications

References 62 publications

Size Dependence of Pd-Catalyzed Hydrogenation of 2,6-Diamino-3,5-dinitropyridine

Size Dependence of Pd-Catalyzed Hydrogenation of 2,6-Diamino-3,5-dinitropyridine

Ni-Modified Ag/SiO2 Catalysts for Selective Hydrogenation of Dimethyl Oxalate to Methyl Glycolate

Kinetics‐assisted identification and regulation of active sites for Pd‐catalyzed propyne selective hydrogenation

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