Direct synthesis of furfuryl alcohol from furfural: catalytic performance of monometallic and bimetallic Mo and Ru phosphides

Bonita, Yolanda; Jain, Varsha; Geng, Feiyang; O’Connell, Timothy P.; Wilson, Woodrow N; Rai, Neeraj; Hicks, Jason C.

doi:10.1039/c9cy00705a

Cited by 39 publications

(34 citation statements)

References 96 publications

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“…Moreover, TPR of C 6 H 6 also suggests that P atoms significantly decrease the C 6 H 6 binding energy and extent of C 6 H 6 decomposition in comparison to Ru(0001), which can promote C 6 H 6 desorption over decomposition and lead to decreased coking during TPR of C 6 H 10 (Figure S3). While these results indicate that the presence of P atoms within the P 0.4 -Ru(0001) surface withdraw charge from Ru atoms, consistent with XPS of related TMP nanoparticles, − Muetterties et al demonstrated that adsorption of trimethyl phosphine could liberate reactive intermediates of dehydrogenation reactions from Ni , and Pt surfaces. To further understand the dehydrogenation selectivity and intrinsic barriers, we probe the mechanism of C 6 H 10 dehydrogenation over Ru(0001) and P 0.4 -Ru(0001).…”

Section: Resultsmentioning

confidence: 68%

“…Previously reported Bader charge analysis and differences among core-electron binding energies detected by X-ray photoelectron spectroscopy (XPS) and X-ray absorption near-edge structure demonstrate that charge transfers from transition metals to P in TMP, which results in electronic modifications of the transitions metals. − These electronic modifications decrease the binding energy of the dehydrogenation product and facilitate the desorption of olefins over further dehydrogenation. In addition, these electronic changes − can modify the binding modes and configuration of surface intermediates caused by interactions with cationic metal and anionic P atoms exposed at surfaces. ,, …”

Section: Introductionmentioning

confidence: 99%

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The Effects of P-Atoms on the Selective Dehydrogenation of C₆H₁₀ over Model Ru Surfaces

2020

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The incorporation of phosphorus into the Ru(0001) surface increases the selectivity of cyclohexene (C6H10) dehydrogenation to benzene (C6H6) by 100-fold when compared to Ru(0001) under steady-state conditions. We propose a series of elementary steps for the reactions of C6H10 over Ru(0001) and P0.4-Ru(0001) based on temperature-programmed reaction (TPR) of C6H10, 1,3-cyclohexadiene and reactive molecular beam scattering (RMBS) of C6H10 on Ru(0001) and P0.4-Ru(0001). TPR of 1,3-cyclohexadiene shows that P atoms alter the kinetically relevant step for C6H10 dehydrogenation from C–H activation in 1,3-cyclohexadiene on Ru(0001) to C–H activation in 2-cyclohexenyl on P0.4-Ru(0001). During TPR of C6H10, C6H6 forms over P0.4-Ru(0001) with an intrinsic activation energy that is 40 kJ mol–1 lower than that for Ru(0001). In addition, the presence of P atoms increases the apparent activation energy for deactivation by 21 kJ mol–1 during RMBS of C6H10. The increase in the barrier for deactivation, presumably by C–C bond rupture steps, significantly reduces the quantity of coke formed by consecutive TPR of C6H10 and contributes to greater selectivities for C6H6 formation. These observations suggest that the addition of P atoms to Ru(0001) introduces both electronic and geometric effects that alter the metal–adsorbate interactions. These findings indicate that transition-metal phosphides may be useful for selective dehydrogenation reactions important for reforming light hydrocarbons (e.g., ethane, propane, and cycloalkanes) to increase the yield of valuable alkenes and arenes.

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Section: Resultsmentioning

confidence: 68%

Section: Introductionmentioning

confidence: 99%

The Effects of P-Atoms on the Selective Dehydrogenation of C₆H₁₀ over Model Ru Surfaces

2020

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“…Current research in this area is focusing on the one-pot preparation of FAL from biomass, crude FUR as feedstock, and developing eco-friendly catalysts for this transformation [43]. There are dedicated reviews available on FAL; therefore, the readers are referred to those for comprehensive information [44,45].…”

Section: Catalytic Reduction Of Furfurals To Furanic Compoundsmentioning

confidence: 99%

Energy Densification of Biomass-Derived Furfurals to Furanic Biofuels by Catalytic Hydrogenation and Hydrodeoxygenation Reactions

Vinod¹,

Dutta²

2021

Sustainable Chemistry

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The concomitant hydrolysis and dehydration of biomass-derived cellulose and hemicellulose to furfural (FUR) and 5-(hydroxymethyl)furfural (HMF) under acid catalysis allows a dramatic reduction in the oxygen content of the parent sugar molecules with a 100% carbon economy. However, most applications of FUR or HMF necessitate synthetic modifications. Catalytic hydrogenation and hydrogenolysis have been recognized as efficient strategies for the selective deoxygenation and energy densification of biomass-derived furfurals generating water as the sole byproduct. Efficient and eco-friendly catalysts have been developed for the selective hydrogenation of furfurals affording renewable furanic compounds such as 2-methylfuran, 2,5-dimethylfuran and 2-methyltetrahydrofuran with potential applications as biofuel, solvent and chemical feedstock. Hydrogen gas or hydrogen donor molecules, required for the above processes, can also be renewably obtained from biomass using catalytic processes, enabling a circular economy. In this review, the recent developments in the energy densification of furfurals to furanic compounds of commercial significance are elaborated, emphasizing the role of catalyst and the reaction parameters employed. Critical discussion on sourcing hydrogen gas required for the processes, using hydrogen donor solvents, catalyst design and the potential markets of furanic intermediates have been made. Critical evaluations of the accomplishments and challenges in this field are also provided.

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“…The authors claimed that not only FUR can be hydrogenated to FuOH in this system, but various unsaturated aldehydes can be transformed to the corresponding unsaturated alcohols due to the synergy created between Ir metal and ReO x , which increases the selectivity and activity without losing the activity of the noble metals. Bonita et al [128] compared the conversion of FUR and the selectivity to FuOH in isopropanol, toluene and hexanes. It was noted that the FUR conversion and the selectivity to FuOH declined significantly in toluene and hexanes, compared to the system involving isopropanol.…”

Section: Effect Of Solvents In the Formation Of Furfuryl Alcoholmentioning

confidence: 99%

Towards the Green Synthesis of Furfuryl Alcohol in A One-Pot System from Xylose: A Review

Millán

Sixta

2020

Catalysts

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In the pursuit of establishing a sustainable biobased economy, valorization of lignocellulosic biomass is increasing its value as a feedstock. Nevertheless, to achieve the integrated biorefinery paradigm, the selective fractionation of its complex matrix to its single constituents must be complete. This review presents and examines the novel catalytic pathways to form furfuryl alcohol (FuOH) from xylose in a one-pot system. This production concept takes on chemical, thermochemical and biochemical transformations or a combination of them. Still, the bulk of the research is targeted to develop heterogeneous catalytic systems to synthesize FuOH from furfural and xylose. The present review includes an overview of the economic aspects to produce this platform chemical in an industrial manner. In the last section of this review, an outlook and summary of catalytic processes to produce FuOH are highlighted.

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Direct synthesis of furfuryl alcohol from furfural: catalytic performance of monometallic and bimetallic Mo and Ru phosphides

Abstract: The catalytic properties of monometallic and bimetallic Ru and Mo phosphides were evaluated for their ability to selectively hydrogenate furfural to furfuryl alcohol.

Cited by 39 publications

References 96 publications

The Effects of P-Atoms on the Selective Dehydrogenation of C₆H₁₀ over Model Ru Surfaces

The Effects of P-Atoms on the Selective Dehydrogenation of C₆H₁₀ over Model Ru Surfaces

Energy Densification of Biomass-Derived Furfurals to Furanic Biofuels by Catalytic Hydrogenation and Hydrodeoxygenation Reactions

Towards the Green Synthesis of Furfuryl Alcohol in A One-Pot System from Xylose: A Review

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Direct synthesis of furfuryl alcohol from furfural: catalytic performance of monometallic and bimetallic Mo and Ru phosphides

Abstract: The catalytic properties of monometallic and bimetallic Ru and Mo phosphides were evaluated for their ability to selectively hydrogenate furfural to furfuryl alcohol.

Cited by 39 publications

References 96 publications

The Effects of P-Atoms on the Selective Dehydrogenation of C6H10 over Model Ru Surfaces

The Effects of P-Atoms on the Selective Dehydrogenation of C6H10 over Model Ru Surfaces

Energy Densification of Biomass-Derived Furfurals to Furanic Biofuels by Catalytic Hydrogenation and Hydrodeoxygenation Reactions

Towards the Green Synthesis of Furfuryl Alcohol in A One-Pot System from Xylose: A Review

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The Effects of P-Atoms on the Selective Dehydrogenation of C₆H₁₀ over Model Ru Surfaces

The Effects of P-Atoms on the Selective Dehydrogenation of C₆H₁₀ over Model Ru Surfaces