More accurate depiction of adsorption energy on transition metals using work function as one additional descriptor

Shen, Xiaochen; Pan, Yanbo; Liu, Bin; Yang, Jinlong; Zeng, Jie; Peng, Zhenmeng

doi:10.1039/c7cp01817g

Cited by 53 publications

(38 citation statements)

References 30 publications

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“…Losiewicz et al investigated the catalytic activity of different metals in the hydrogen electroevolution exchange current using the work function as an activity descriptor proving that the catalytic activity is a periodic function of their atomic numbers [59]. Likewise, Shen et al used Φ as an additional descriptor along with the d-band centre to improve the predicting accuracy and to understand the catalytic properties in oxygen reduction reactions [60]. They considered the fact that band hybridisation and electron transfer can occur at the same time when a molecule adsorbs on TMs.…”

Section: Scheme 1 Hydrodeoxygenation (Hdo) Reaction Scheme Of Guaiacol To Benzene Water and Methanolmentioning

confidence: 99%

Biomass hydrodeoxygenation catalysts innovation from atomistic activity predictors

Morteo-Flores

Engel

Roldán

2020

Phil. Trans. R. Soc. A.

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Circular economy emphasizes the idea of transforming products involving economic growth and improving the ecological system to reduce the negative consequences caused by the excessive use of raw materials. This can be achieved with the use of second-generation biomass that converts industrial and agricultural wastes into bulk chemicals. The use of catalytic processes is essential to achieve a viable upgrade of biofuels from the lignocellulosic biomass. We carried out density functional theory calculations to explore the relationship between 13 transition metals (TMs) properties, as catalysts, and their affinity for hydrogen and oxygen, as key species in the valourization of biomass. The relation of these parameters will define the trends of the hydrodeoxygenation (HDO) process on biomass-derived compounds. We found the hydrogen and oxygen adsorption energies in the most stable site have a linear relation with electronic properties of these metals that will rationalize the surface's ability to bind the biomass-derived compounds and break the C–O bonds. This will accelerate the catalyst innovation for low temperature and efficient HDO processes on biomass derivates, e.g. guaiacol and anisole, among others. Among the monometallic catalysts explored, the scaling relationship pointed out that Ni has a promising balance between hydrogen and oxygen affinities according to the d -band centre and d -band width models. The comparison of the calculated descriptors to the adsorption strength of guaiacol on the investigated surfaces indicates that the d -band properties alone are not best suited to describe the trend. Instead, we found that a linear combination of work function and d -band properties gives significantly better correlation. This article is part of a discussion meeting issue ‘Science to enable the circular economy’.

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Section: Scheme 1 Hydrodeoxygenation (Hdo) Reaction Scheme Of Guaiacol To Benzene Water and Methanolmentioning

confidence: 99%

Biomass hydrodeoxygenation catalysts innovation from atomistic activity predictors

Morteo-Flores

Engel

Roldán

2020

Phil. Trans. R. Soc. A.

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“…To understand the origin of the hydrogen adsorption energies and HER activity of the present SACs, we considered the d band center, the lowest unoccupied state energy (E lus ), and the ionic energy (E ionic ) ,. The ionic energy E ionic was calculated by the work function of the SACs (E ionic =Δq ⋅ ΔΦ=Δq ⋅ (Φ SAC −Φ H ); Δq: charge transfer, Φ: workfunction),, an approximate measure of charge transfer between SACs and adsorbed hydrogen atom . As shown in Figure , we find no linear correlation between the calculated hydrogen adsorption energies on SACs vs. d band center (as in literature) or lowest unoccupied state energy.…”

Section: Resultsmentioning

confidence: 99%

Ultralow Overpotential of Hydrogen Evolution Reaction using Fe‐Doped Defective Graphene: A Density Functional Study

et al. 2018

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We report great promises of single (transition metal) atom catalysts (SACs) anchored to single-and double-vacancy sites of the defective graphene structures for hydrogen evolution reaction (HER). Among 120 candidates with all 3d, 4d, and 5dblock transition metals considered, the inexpensive Fe-based SAC catalyst shows a theoretical overpotential of 5 mV, the lowest value reported to date theoretically or experimentally.With the help of various electronic structural analysis, we reveal that the key to the observed superior HER activity of Fe-based SAC is the enhanced ionicity of bonding between hydrogen and the corresponding SAC and the lack of ensemble effect that causes the *H binding weaker to be nearly at the top of the HER activity volcano.

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“…Our previous study has discovered a linear correlation of charge transfer and a quadratic correlation of adsorption energy with work function of catalyst for describing molecule‐catalyst interaction following ionic bonding mechanism . Considering the discovered linear correlation between adsorption energy and activation energy barrier and the fact that ionic bonding dominates molecule‐oxide interactions, the energy barriers associated with CO oxidation elementary steps would be largely describable as (see Supporting Information for details) [Equations (1)–]:

true E_{a, T S 1} = A_{1} \times ([] \frac{(() \emptyset_{C O 2} + \emptyset_{C O})}{2} - (W_{{M O}_{x}} - \frac{Δ W}{2})) \times ({Δ W + \emptyset}_{C O 2} - \emptyset_{C O})

true E_{a, T S 2} = A_{2} \times ([] (W_{{M O}_{x}} - \frac{Δ W}{2}) + \frac{(() \emptyset_{C O} - \emptyset_{C O 2} - \emptyset_{O 2})}{2}) \times (Δ W - \emptyset_{C O 2} - \emptyset_{C O} + \emptyset_{O 2})

…”

Section: Figurementioning

confidence: 99%

Oscillation of Work Function during Reducible Metal Oxide Catalysis and Correlation with the Activity Property

et al. 2019

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Deducing from the fact that RMO catalysis typically involves reversible valence states transformation of active sites, we report one new model that uses RMO work function and its oscillation as descriptors to depict the activity property. Our experiments and DFT simulations of CO oxidation model reaction lead to an inverted volcano correlation between the two descriptors and the activity energy barrier, which shows good consistence with this new model and thus validates its effectiveness. The findings of work function and the oscillation as governing structural parameters provide a plausible theory to understand RMO catalysis and guide the catalyst research.

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More accurate depiction of adsorption energy on transition metals using work function as one additional descriptor

Cited by 53 publications

References 30 publications

Biomass hydrodeoxygenation catalysts innovation from atomistic activity predictors

Biomass hydrodeoxygenation catalysts innovation from atomistic activity predictors

Ultralow Overpotential of Hydrogen Evolution Reaction using Fe‐Doped Defective Graphene: A Density Functional Study

Oscillation of Work Function during Reducible Metal Oxide Catalysis and Correlation with the Activity Property

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