Selectivity of the First Two Glycerol Dehydrogenation Steps Determined Using Scaling Relationships

Valter, Mikael; Santos, Egon Campos dos; Pettersson, Lars; Hellman, Anders

doi:10.1021/acscatal.0c04186

Cited by 29 publications

(34 citation statements)

References 60 publications

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“…These measurements agree with assumptions made in kinetic studies that sought to explain differences in apparent E a for hydrogenolysis of alkanes under conditions that H* was the MARI and transition states formed only after the desorption of several H*-atoms, consistent with results from DFT calculations. , Our group reported that activation barriers for alkene epoxidation on various metal-incorporated BEA (M-BEA) catalysts correlate linearly with adsorption enthalpies of the corresponding epoxide measured by isothermal titration calorimetry . We anticipate that appropriate microcalorimetry experiments (e.g., enthalpies of dissociative adsorption of small alcohols or aldehydes) would be useful in the development of accurate scaling relationships, as shown computationally by Valter et al…”

Section: Discussionmentioning

confidence: 99%

“…demonstrated that binding energies of CH 3 O* or CH 2 OH* intermediates obtained from DFT calculations describe rates for the dehydrogenation of glycerol on metals’ surfaces (Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, etc.) better than BE M‑O or BE M‑C . These comparisons indicate that the binding mode of the molecular fragments (i.e., μ 3 -C atoms compared to η 1 (C)–CH 2 OH*) and interactions between moieties of the adsorbed species (e.g., hydroxyl groups) and the surface significantly influence the stability of these complexes and much be considered for accurate predictions.…”

Section: Hydrogenolysis Of Biomass-derived Oxygenatesmentioning

confidence: 93%

“…better than BE M-O or BE M-C . 91 These comparisons indicate that the binding mode of the molecular fragments (i.e., μ 3 -C atoms compared to η 1 (C)−CH 2 OH*) and interactions between moieties of the adsorbed species (e.g., hydroxyl groups) and the surface significantly influence the stability of these complexes and much be considered for accurate predictions.…”

Section: Hydrogenolysis Of Biomassmentioning

confidence: 99%

See 2 more Smart Citations

Advances in Understanding the Selective Hydrogenolysis of Biomass Derivatives

2021

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Biomass has attracted great attention as an alternative to petrochemicals for the production of valuable chemicals and fuels. Hydrogenolysis reactions over heterogeneous catalysts offer pathways to upgrade renewable compounds to a variety of building block molecules; however, similarities among the functional groups in these reactants frequently limit the selectivity of these reactions. Consequently, a fundamental understanding of how oxygenates adsorb, activate, and react upon solid surfaces is essential for catalyst design and reaction engineering. In this Perspective, we describe significant advances in knowledge of the reaction networks and mechanisms, key reactive intermediates, and active site motifs that allow for the selective production of desired compounds by hydrogenolysis over heterogeneous catalysts. These insights draw from the mechanistic understanding gained from comparisons between kinetic measurements, in situ characterization of catalysts and organic intermediates, and ab initio calculations. Drawing from detailed insight taken from a century of study into reactions of hydrogen with hydrocarbons, we discuss the molecular similarities between reactions that cleave C−O and C−C bonds during hydrogenolysis of biomass-derived compounds that range from simple (e.g., alcohols) to polyfunctional molecules (e.g., guaiacol) on monometallic, bimetallic, and nonmetallic catalysts. Finally, we describe current challenges and opportunities for future research into hydrogenolysis reactions.

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Section: Discussionmentioning

confidence: 99%

Section: Hydrogenolysis Of Biomass-derived Oxygenatesmentioning

confidence: 93%

Section: Hydrogenolysis Of Biomassmentioning

confidence: 99%

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Advances in Understanding the Selective Hydrogenolysis of Biomass Derivatives

2021

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“…Furthermore, oxidation of DHA leads to the formation of HPA, while GLAD can be oxidized to GLA and then to GA and FA by breaking the C–C bond. At this stage, it is not clear why the secondary hydroxyl group is the preferred oxidation site, and a full understanding of the oxidation pathway may require a thorough theoretical inspection, which is still under-developed due to the complicated oxidation intermediary steps and a large number of possible products, even on noble metal catalysts …”

Section: Resultsmentioning

confidence: 99%

“…At this stage, it is not clear why the secondary hydroxyl group is the preferred oxidation site, and a full understanding of the oxidation pathway may require a thorough theoretical inspection, which is still under-developed due to the complicated oxidation intermediary steps and a large number of possible products, even on noble metal catalysts. 47 Nevertheless, our work opens a new door toward selective electrochemical oxidation of glycerol to value-added chemicals using noble metal-free electrocatalysts, with a large library of potential electrocatalysts being developed for water oxidation reactions to choose from. 48−50 Our preliminary results show that similar EGOR activity and enhancement were also achieved on the electrodeposited Ni−B i /CF electrode.…”

Section: And B(oh)mentioning

confidence: 99%

Electrochemical Oxidation of Glycerol to Dihydroxyacetone in Borate Buffer: Enhancing Activity and Selectivity by Borate–Polyol Coordination Chemistry

Huang

Zou

Jiang

2021

ACS Sustainable Chem. Eng.

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Selective electrochemical oxidation of glycerol, the major byproduct during the biodiesel production process, can not only make biodiesel production more environmentally benign and economically feasible but also generate value-added C3 chemicals that are important for medicinal and cosmetics applications. However, severe C–C bond breakage often occurs, which would lead to low C3 selectivity, especially on earth-abundant, low-cost transition metal electrocatalysts. In this study, by exploiting the coordination ability of borate ions with polyol molecules, we report enhanced and selective electrochemical oxidation of glycerol to ∼85% C3 chemicals (67% for dihydroxyacetone in detected liquid products, with an average production rate of 90 mmol m–2 h–1), using cobalt borate as the electrocatalyst in borate buffer electrolyte. The improved electrochemical activity and selectivity at different borate buffer concentrations and solution pH values have been explicitly correlated with the coordination ability of borate with glycerol under different circumstances, as revealed by 11B NMR spectroscopy studies. The strategy presented herein can be potentially extended to the selective upgrading of a broad scope of biomass-derived sugars and polyols, for producing value-added chemicals on low-cost non-noble metal electrocatalysts.

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Carbon‐zero co‐production of hydrogen and chemicals boosted by directional hydrogen spillover via terminated interface

Guo,

Wu,

Zhao

et al. 2024

AIChE Journal

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Acceptorless dehydrogenation of biomass‐alcohol provides an appealing route for co‐producing green H2 and high‐value chemicals. However, the sluggish H species binding step severely inhibits reaction equilibrium and cause C‐C cleavage. Herein, we propose a unique directional H spillover strategy driven by controlling electron transport direction via constructing Au‐O‐Cu‐O‐Mg/Al interfacial structure, to allow H species transfer from O‐H dehydrogenation Cu2+ site to C‐H dehydrogenation Au site to promote H2 formation. The structure that each Cu precisely terminated by Mg/Al is inherited from layered double hydroxides with orderly dispersed atom arrangement. Comprehensive studies substantiate that the unreducible Mg2+/Al3+ blocks electron transfer toward support, whereas Au‐O‐Cu electronic interaction drives H spillover from the support to Au. The Au/CuMgAl catalyst demonstrated unprecedentedly high glycerol dehydrogenation activity, showing 3–10 times turnover frequency (1.18 × 104 h−1) than other biomass‐derived H2 formation system, co‐producing lactic acid with selectivity up to 98.8%.

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Selectivity of the First Two Glycerol Dehydrogenation Steps Determined Using Scaling Relationships

Cited by 29 publications

References 60 publications

Advances in Understanding the Selective Hydrogenolysis of Biomass Derivatives

Advances in Understanding the Selective Hydrogenolysis of Biomass Derivatives

Electrochemical Oxidation of Glycerol to Dihydroxyacetone in Borate Buffer: Enhancing Activity and Selectivity by Borate–Polyol Coordination Chemistry

Carbon‐zero co‐production of hydrogen and chemicals boosted by directional hydrogen spillover via terminated interface

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