High-pressure vapor-phase hydrodeoxygenation of lignin-derived oxygenates to hydrocarbons by a PtMo bimetallic catalyst: Product selectivity, reaction pathway, and structural characterization

Yohe, Sara L.; Choudhari, Harshavardhan; Mehta, Dhairya D.; Dietrich, Paul J.; Detwiler, Michael D.; Akatay, Cem; Stach, Eric A.; Miller, Jeffrey T.; Delgass, W. Nicholas; Agrawal, Rakesh; Ribeiro, Fabio H.

doi:10.1016/j.jcat.2016.10.009

Cited by 62 publications

(22 citation statements)

References 55 publications

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“…Experimental results and DFT calculation indicated that Mo sites on the surface of PtMo significantly lower the energy barrier for m ‐cresol tautomerization and subsequent deoxygenation process, resulting the introduction of tautomerization‐deoxygenation pathway for PtMo catalyst in contrast to the ring hydrogenation pathway over Pt catalyst . PtMo/MWCNT catalyst employed in HDO of dihydroeugenol, a more complicate lignin‐derived monomers, showed high activity, with unprecedented high yield of hydrocarbon propylcyclohexane (yield≈98 %) . The reaction pathways in PtMo/MWCNT catalytic system is presented in Figure .…”

Section: Hydrodeoxygenation Using H2mentioning

confidence: 99%

Catalytic Upgrading of Biomass Model Compounds: Novel Approaches and Lessons Learnt from Traditional Hydrodeoxygenation – a Review

et al. 2019

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Catalytic hydrodeoxygenation (HDO) is a fundamental process for bio-resources upgrading to produce transportation fuels or added value chemicals. The bottleneck of this technology to be implemented at commercial scale is its dependence on high pressure hydrogen, an expensive resource which utilization also poses safety concerns. In this scenario, the development of hydrogen-free alternatives to facilitate oxygen removal in biomass derived compounds is a major challenge for catalysis science but at the same time it could revolutionize biomass processing technologies. In this review we have analysed several novel approaches, including catalytic transfer hydrogenation (CTH), combined reforming and hydrodeoxygenation, metal hydrolysis and subsequent hydrodeoxygenation along with non-thermal plasma (NTP) to avoid the supply of external H 2 . The knowledge accumulated from traditional HDO sets the grounds for catalysts and processes development among the hydrogen alternatives. In this sense, mechanistic aspects for HDO and the proposed alternatives are carefully analysed in this work. Biomass model compounds are selected aiming to provide an in-depth description of the different processes and stablish solid correlations catalysts composition-catalytic performance which can be further extrapolated to more complex biomass feedstocks. Moreover, the current challenges and research trends of novel hydrodeoxygenation strategies are also presented aiming to spark inspiration among the broad community of scientists working towards a low carbon society where bio-resources will play a major role. Figure 1. Three basic phenylpropane monomers: (1) p-coumaryl alcohol; (2) coniferyl alcohol; (3) sinapyl alcohol.

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Section: Hydrodeoxygenation Using H2mentioning

confidence: 99%

Catalytic Upgrading of Biomass Model Compounds: Novel Approaches and Lessons Learnt from Traditional Hydrodeoxygenation – a Review

et al. 2019

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“…While different catalysts including metals [2][3][4][5][6][7][8][9][10][11], metal sulfides [12][13][14], metal phosphides [15][16][17][18][19] and metal carbides [20][21][22] have been investigated in the HDO process, the supported metal catalysts such as Pt, Pd, Ru and Fe have been shown to be promising for the hydrodeoxygenation reactions of phenolic compounds [2][3][4][5][6][7][8][9][10]. Various aspects of the metal catalysts such as the incorporation of bifunctionality [23][24][25][26][27][28][29][30][31], use of bimetallics, [32][33][34][35][36][37][38] and metal-support effects [39][4...…”

Section: Introductionmentioning

confidence: 99%

Mechanistic analysis of the role of metal oxophilicity in the hydrodeoxygenation of anisole

Tan

Wang

Long

et al. 2017

Journal of Catalysis

118

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A combined experimental and theoretical comparative study of the hydrodeoxygenation (HDO) of anisole was conducted over Pt, Ru, and Fe metals. In the experimental part, an inert silica support was used to directly compare the catalytic activity and selectivity of the three metals at 375 ºC under H 2 flow at atmospheric pressure. In parallel, for density functional theory (DFT) calculations the close-packed Pt(111), Ru(0001), and Fe(110) surfaces were employed to compare the possible mechanisms on these metals. It was observed that over Pt/SiO 2 and Ru/SiO 2 catalysts, both phenol and benzene were the major products in a phenol/benzene ratio that decreased with the level of conversion. By contrast, over the Fe/SiO 2 catalyst, no phenol formation was detected, even at low conversions. The DFT results show that over all the three metal surfaces the dehydrogenation at the-CH 3 side group occurs before the CO bond breaking. This removal of H atoms from the-CH 3 group facilitates the activation of the aliphatic C alkyl-O bond. Therefore, it can be concluded that a common intermediate for the three metals is a surface phenoxy and the significant differences between the three metals is related to the reactivity of this surface phenoxy. That is, over Pt(111) and Ru(0001) the phenoxy intermediate is hydrogenated to phenol, which in turn, can undergo further HDO to form benzene. This result is in agreement with the experiments over Pt/SiO 2 and Ru/SiO 2 catalysts. Over these catalysts, both phenol and benzene are major products, with the selectivity to benzene increasing with conversion at the expense of phenol. In contrast, over the Fe(110) surface, the strong metal oxophilicity makes the direct cleavage of the CO bond in the surface phenoxy easier than

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“…Noble metals such as Pt [175,196,201,271,[276][277][278][279][280][281][282], Pd [185,196,206,274,275,281,[283][284][285][286], and…”

Section: Noble Metalsmentioning

confidence: 99%

Transportation fuels from biomass fast pyrolysis, catalytic hydrodeoxygenation, and catalytic fast hydropyrolysis

Dabros¹,

Stummann²,

Høj³

et al. 2018

Progress in Energy and Combustion Science

228

147

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High-pressure vapor-phase hydrodeoxygenation of lignin-derived oxygenates to hydrocarbons by a PtMo bimetallic catalyst: Product selectivity, reaction pathway, and structural characterization

Cited by 62 publications

References 55 publications

Catalytic Upgrading of Biomass Model Compounds: Novel Approaches and Lessons Learnt from Traditional Hydrodeoxygenation – a Review

Catalytic Upgrading of Biomass Model Compounds: Novel Approaches and Lessons Learnt from Traditional Hydrodeoxygenation – a Review

Mechanistic analysis of the role of metal oxophilicity in the hydrodeoxygenation of anisole

Transportation fuels from biomass fast pyrolysis, catalytic hydrodeoxygenation, and catalytic fast hydropyrolysis

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