Reaction pathway for partial hydrogenation of 1,3-butadiene over Pt/SiO<sub>2</sub>

Hu, Chaoquan; Sun, Jiahan; Yang, Yafeng; Zhu, Qingshan; Yu, Bin

doi:10.1039/c7cy01882g

Cited by 19 publications

(12 citation statements)

References 38 publications

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“…These above phenomena are consistent with the catalytic evaluation. According to reported literature, , with respect to di-σ adsorption at continuous sites, CC bond is adsorbed on isolated atoms in π-bound configuration to form a vinyl species, which is easily hydrogenated to produce the ethylene with low desorption energy.…”

Section: Resultsmentioning

confidence: 99%

Highly Selective and Stable Isolated Non-Noble Metal Atom Catalysts for Selective Hydrogenation of Acetylene

McCue

Liu

et al. 2021

ACS Catal.

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A strategy to fabricate a stable and site-isolated Ni catalyst is reported. Specifically, Mo 3 S 4 clusters allowed individual Ni atoms to bond with Mo and S to create a type of active site. A site-isolated Ni 1 MoS/Al 2 O 3 sample exhibited high performance in the selective hydrogenation of acetylene. Concretely, 90% ethylene selectivity was achievable at full acetylene conversion under relatively mild reaction conditions without any obvious decay in performance observed during longer testing periods. In contrast, a reference catalyst with Ni ensembles exhibited poor selectivity and stability. Density functional theory (DFT) calculations suggested that H 2 molecules were activated by a heterolytic route over Ni 1 MoS/Al 2 O 3 , which enhanced the reaction rate. Improved selectivity originated from the unique isolated Ni δ+ structure induced by Mo and S, which facilitated product desorption as opposed to overhydrogenation or oligomerization. This work provides a feasible way to construct site-isolated catalysts with higher active metal loadings and opens up an opportunity for selective hydrogenation.

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Section: Resultsmentioning

confidence: 99%

Highly Selective and Stable Isolated Non-Noble Metal Atom Catalysts for Selective Hydrogenation of Acetylene

McCue

Liu

et al. 2021

ACS Catal.

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“…Many past studies have focused on the hydrogenation of ethene, where no allylic position is present. − However, the importance of the allylic proton has been seen in 1,3-butadiene hydrogenation ,,, and alkene epoxidation via an enhanced reactivity of allylic protons in elementary dehydrogenation and hydrogenation steps. Moreover, the proposed mechanism was already reported for double-bond isomerization in the absence of hydrogen on homogeneous Pd catalysts as well as supported Pd particles. − In fact, the allyl adsorbate was experimentally confirmed to exist on the catalyst surface .…”

Section: Summary and Commentmentioning

confidence: 99%

Catalytic Transformations of 1-Butene over Palladium. A Combined Experimental and Theoretical Study

et al. 2018

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Applying a density functional approach to slab models of planar, (111), and rough, (110), Pd surfaces, we determined the isomerization free energy barriers of 1-butene to be significantly lower than the hydrogenation barriers. Microkinetic modeling allows one to mirror the kinetic experiments on conversions of 1-butene at the corresponding single-crystal surfaces in a qualitative fashion. Despite the inherent limitations of such kinetic modeling, theoretical predictions are fully supported by experimental data using Pd model catalysts: i.e., Pd(111) and Pd(110) surfaces. The isomerization mechanism was calculated to proceed via an initial dehydrogenation of 1-butene to 1-buten-3-yl as an intermediatein contrast to the commonly proposed 2-butyl intermediate, associated with the Horiuti–Polanyi mechanism. Our modeling results rule out the original assumption that isomerization has to start with a hydrogenation step to rationalize the dependence of isomerization on hydrogen. However, this hydrogen dependence may arise in the second step, after an initial dehydrogenation, as suggested by the experimental data under hydrogen-deficient conditions.

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“…The accumulation of these benzene oxidation intermediates was noted with PdAg/Fe 2 O 3 , while their production was much lower than with Fe 2 O 3 , Ag/Fe 2 O 3 , or Pd/Fe 2 O 3 in a temperature range from 100 to 300 °C. In addition, the bands associated with light olefins such as hexene (3012, 2975, and 1645 cm –1 ) and butene (3100, 3018, and 1645 cm –1 ) were also present at temperatures above 100 °C, 100 °C, 150 °C, and 150 °C for PdAg/Fe 2 O 3 , Ag/Fe 2 O 3 , Pd/Fe 2 O 3 , and Fe 2 O 3 , respectively, further illustrating the excellent low-temperature catalytic cracking capability of PdAg/Fe 2 O 3 . Other intermediates, such as formic acid (3150, 1712, 1430, and 1270 cm –1 ), formate (1550 and 1353 cm –1 ), , methyl alcohol (3335, 1400, and 1030 cm –1 ), and formaldehyde (1721 and 1019 cm –1 ), , derived from the oxidation of light olefins and aromatic species, were all also produced by all samples.…”

Section: Resultsmentioning

confidence: 87%

Efficient Catalytic Combustion of Cyclohexane over PdAg/Fe₂O₃ Catalysts under Low-Temperature Conditions: Establishing the Degradation Mechanism Using PTR-TOF-MS and in Situ DRIFTS

Wen

Guo

et al. 2022

ACS Appl. Mater. Interfaces

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Cyclohexane, a typical volatile organic compound (VOC), poses high risks to the environment and humans. Herein, synthesized PdAg/Fe2O3 catalysts exhibited exceptional catalytic performance for cyclohexane combustion at lower temperatures (50% mineralization temperature (T 50) of 199 °C, 90% mineralization temperature (T 90) of 315 °C) than Pd/Fe2O3 (T 50 of 262 °C, T 90 of 335 °C) and Fe2O3 (T 50 of 305 °C, T 90 of 360 °C). In addition, PdAg/Fe2O3 displayed enhanced stability by alloying Ag with Pd. The redox and acidity of the PdAg/Fe2O3 were studied by XPS, H2-TPR, and NH3-TPD. In situ diffuse reflectance infrared Fourier transform spectroscopy and proton-transfer-reaction time-of-flight mass spectrometry were applied to identify the intermediates formed on the catalyst surface and in the tail gas during oxidation, respectively. Results suggested that loading PdAg onto Fe2O3 significantly enhanced the adsorption and activation of oxygen and cyclohexane, oxidative dehydrogenation of cyclohexane to benzene, and catalytic cracking of cyclohexane to olefins at low temperatures. This in-depth study will benefit the design and application of efficient catalysts for the effective combustion of VOCs at low temperatures.

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Reaction pathway for partial hydrogenation of 1,3-butadiene over Pt/SiO₂

Abstract: The reaction pathway for partial hydrogenation of 1,3-butadiene over a Pt/SiO2 catalyst was explored with a combination of in situ diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy, intrinsic kinetics, and density functional theory (DFT) calculations.

Cited by 19 publications

References 38 publications

Highly Selective and Stable Isolated Non-Noble Metal Atom Catalysts for Selective Hydrogenation of Acetylene

Highly Selective and Stable Isolated Non-Noble Metal Atom Catalysts for Selective Hydrogenation of Acetylene

Catalytic Transformations of 1-Butene over Palladium. A Combined Experimental and Theoretical Study

Efficient Catalytic Combustion of Cyclohexane over PdAg/Fe₂O₃ Catalysts under Low-Temperature Conditions: Establishing the Degradation Mechanism Using PTR-TOF-MS and in Situ DRIFTS

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Reaction pathway for partial hydrogenation of 1,3-butadiene over Pt/SiO2

Abstract: The reaction pathway for partial hydrogenation of 1,3-butadiene over a Pt/SiO2 catalyst was explored with a combination of in situ diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy, intrinsic kinetics, and density functional theory (DFT) calculations.

Cited by 19 publications

References 38 publications

Highly Selective and Stable Isolated Non-Noble Metal Atom Catalysts for Selective Hydrogenation of Acetylene

Highly Selective and Stable Isolated Non-Noble Metal Atom Catalysts for Selective Hydrogenation of Acetylene

Catalytic Transformations of 1-Butene over Palladium. A Combined Experimental and Theoretical Study

Efficient Catalytic Combustion of Cyclohexane over PdAg/Fe2O3 Catalysts under Low-Temperature Conditions: Establishing the Degradation Mechanism Using PTR-TOF-MS and in Situ DRIFTS

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Reaction pathway for partial hydrogenation of 1,3-butadiene over Pt/SiO₂

Efficient Catalytic Combustion of Cyclohexane over PdAg/Fe₂O₃ Catalysts under Low-Temperature Conditions: Establishing the Degradation Mechanism Using PTR-TOF-MS and in Situ DRIFTS