Surface modification processes during methane decomposition on Cu-promoted Ni–ZrO<sub>2</sub>catalysts

Wolfbeisser, Astrid; Klötzer, Bernhard; Mayr, Lukas; Rameshan, Raffael; Zemlyanov, Dmitry; Bernardi, Johannes; Föttinger, Karin; Rupprechter, Günther

doi:10.1039/c4cy00988f

Cited by 50 publications

(41 citation statements)

References 82 publications

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“…Also, reconstruction of the assynthesized catalytic structure under reaction conditions may be expected when significant adsorbate−metal specific interactions exist, for example in a CO atmosphere. 89 However, based on the lack of ring hydrogenation observed in our studies for the Cu−Ni/TiO 2 catalyst, it can be concluded that migration of Ni to the catalyst surface is minimal under reaction conditions.…”

Section: Discussionmentioning

confidence: 60%

Support Induced Control of Surface Composition in Cu–Ni/TiO₂ Catalysts Enables High Yield Co-Conversion of HMF and Furfural to Methylated Furans

et al. 2017

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5-(Hydroxymethyl)furfural (HMF) and furfural (FF) have been identified as valuable biomass-derived fuel precursors suitable for catalytic hydrodeoxygenation (HDO) to produce high octane fuel additives such dimethyl furan (DMF) and methyl furan (MF), respectively. In order to realize economically viable production of DMF and MF from biomass, catalytic processes with high yields, low catalyst costs, and process simplicity are needed. Here, we demonstrate simultaneous coprocessing of HMF and FF over Cu−Ni/ TiO 2 catalysts, achieving 87.5% yield of DMF from HMF and 88.5% yield of MF from FF in a one pot reaction. The Cu−Ni/TiO 2 catalyst exhibited improved stability and regeneration compared to Cu/TiO 2 and Cu/Al 2 O 3 catalysts for FF HDO, with a ∼7% loss in FF conversion over four sequential recycles, compared to a ∼50% loss in FF conversion for Cu/Al 2 O 3 and a ∼30% loss in conversion for Cu/TiO 2. Characterization of the Cu−Ni/TiO 2 catalyst by X-ray photoelectron spectroscopy, scanning transmission electron microscopy, and H 2 −temperature-programmed reduction and comparison to monometallic Cu and Ni on Al 2 O 3 and TiO 2 and bimetallic Cu−Ni/Al 2 O 3 catalysts suggest that the unique reactivity and stability of Cu−Ni/TiO 2 derives from support-induced metal segregation in which Cu is selectively enriched at the catalyst surface, while Ni is enriched at the TiO 2 interface. These results demonstrate that Cu−Ni/TiO 2 catalysts promise to be a system capable of integrating directly with a combined HMF and FF product stream from biomass processing to realize lower cost production of liquid fuels from biomass.

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Section: Discussionmentioning

confidence: 60%

Support Induced Control of Surface Composition in Cu–Ni/TiO₂ Catalysts Enables High Yield Co-Conversion of HMF and Furfural to Methylated Furans

et al. 2017

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“…However, many researchers suggest that the Ni‐based catalysts also favor the CC cleavage, and the deposition of carbon, which is responsible for the rapid deactivation of the catalysts. Combining Ni with a second metal such as Cu was found to enhance not only the performances of the catalyst but also to improve carbon resistance . Besides, combining Ni with two other metals (Sn, K), also yielded improvement of the catalytic performances.…”

Section: Main Challenges and Perspectivesmentioning

confidence: 94%

Catalytic decarboxylation of fatty acids to hydrocarbons over non‐noble metal catalysts: the state of the art

Kiméné

Wojcieszak

Paul

et al. 2018

J of Chemical Tech & Biotech

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The catalytic decarboxylation of fatty acids to yield hydrocarbons, for use as biofuel as a main target, is a topical reaction in which the main challenge is actually to control the selectivity while using the smallest amount of hydrogen possible (or even better, not using hydrogen at all) in order to optimize cost-efficiency of the process. Herein, the focus is on the non-noble mono-, biand tri-metallic catalysts used to carry out this reaction. Historically, several non-noble monometallic catalysts based on Cu, Co, Ni supported on different types of supports were first studied. Among such materials, the Co-based catalysts were not selective, while, Cu-based catalysts were more or less selective to hydrocarbons or to olefins, depending on the support used. Among these three metals, the Ni-based catalysts are the most widely described ones due to their specific ability to promote deoxygenation reactions. Combining Ni to a second metal yielded a synergistic effect toward better catalytic performances, with increases in both conversion and selectivity and also improvement of the resistance of the catalyst to carbon deposit, especially when adding non-noble metals. For future prospects, it appears that the main challenge will be to be able to maintain good catalytic performances under inert gas in solvent-free conditions, in order to yield a fully environmentally friendly and cost-effective process. REFERENCES1 Hermida L, Abdullah AZ and Mohamed AR, Deoxygenation of fatty acid to produce diesel-like hydrocarbons: a review of process conditions, reaction kinetics and mechanism. Renew Sust Energ Rev 42:1223-1233 (2015).

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“…Pd (111)Gabasch et al [129] Ethene oxidationPd(111)Gabasch et al [130] Methaned ecomposition Cu/Ni/ZrO 2 Wolfbeissere tal. [131] CO hydrogenationPd(111)Rupprechter et al [132] Methanol dehydrogenation Pd(111)Morkel et al [133]…”

Section: Methaneo Xidationmentioning

confidence: 99%

Ambient Pressure Photoelectron Spectroscopy: Opportunities in Catalysis from Solids to Liquids and Introducing Time Resolution

2018

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Photoelectron spectroscopy is an excellent technique to explore chemically complex systems in catalysis. However, due to a small mean free path of photoelectrons in gas, liquid, and solid media, the study of the gas–solid, liquid–gas, solid–liquid interfaces, as well as liquid homogeneous systems are a serious challenge. With differentially pumped analyzers this limitation ceases to exist and no longer restricts photoelectron spectroscopy only to ultra‐high vacuum conditions. Presently, photoemission studies at tens of mbar of pressure are possible. To reach atmospheric pressure and even higher, membrane‐covered closed cells have been developed. Graphene membranes are impermeable to molecules and almost transparent to photoelectrons. They are used as a pressure barrier between the enclosed cell at atmospheric pressure and the electron analyzer at vacuum while allowing transmission of photoelectrons. By accessing to atmospheric pressure range, with this kind of cell, photoemission studies will become a versatile in situ and operando tool for catalysis. Studies involving liquids in static conditions are an important aspect in this direction, which can be extended to homogeneous catalytic systems. Liquids are presently accessible using micro‐jets. Another aspect which is of paramount interest to investigate catalysts is time resolution. By improving the time resolution of photoemission measurements to the sub‐second regime it is possible to follow the kinetic changes that are crucial of a catalytic reaction, the changes that occur during catalyst pretreatment and activation, and notably to differentiate active species from spectator ones, which may be the dominating species in a classical experiment.

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Surface modification processes during methane decomposition on Cu-promoted Ni–ZrO₂catalysts

Abstract: We explored the surface chemistry of methane on Cu-promoted Ni–ZrO2 catalysts and observed a limited stability of the CuNi alloy under relevant reaction conditions.

Cited by 50 publications

References 82 publications

Support Induced Control of Surface Composition in Cu–Ni/TiO₂ Catalysts Enables High Yield Co-Conversion of HMF and Furfural to Methylated Furans

Support Induced Control of Surface Composition in Cu–Ni/TiO₂ Catalysts Enables High Yield Co-Conversion of HMF and Furfural to Methylated Furans

Catalytic decarboxylation of fatty acids to hydrocarbons over non‐noble metal catalysts: the state of the art

Ambient Pressure Photoelectron Spectroscopy: Opportunities in Catalysis from Solids to Liquids and Introducing Time Resolution

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Surface modification processes during methane decomposition on Cu-promoted Ni–ZrO2catalysts

Abstract: We explored the surface chemistry of methane on Cu-promoted Ni–ZrO2 catalysts and observed a limited stability of the CuNi alloy under relevant reaction conditions.

Cited by 50 publications

References 82 publications

Support Induced Control of Surface Composition in Cu–Ni/TiO2 Catalysts Enables High Yield Co-Conversion of HMF and Furfural to Methylated Furans

Support Induced Control of Surface Composition in Cu–Ni/TiO2 Catalysts Enables High Yield Co-Conversion of HMF and Furfural to Methylated Furans

Catalytic decarboxylation of fatty acids to hydrocarbons over non‐noble metal catalysts: the state of the art

Ambient Pressure Photoelectron Spectroscopy: Opportunities in Catalysis from Solids to Liquids and Introducing Time Resolution

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Product

Resources

About

Surface modification processes during methane decomposition on Cu-promoted Ni–ZrO₂catalysts

Support Induced Control of Surface Composition in Cu–Ni/TiO₂ Catalysts Enables High Yield Co-Conversion of HMF and Furfural to Methylated Furans

Support Induced Control of Surface Composition in Cu–Ni/TiO₂ Catalysts Enables High Yield Co-Conversion of HMF and Furfural to Methylated Furans