Substantial improvement of electrocatalytic predictions by systematic assessment of solvent effects on adsorption energies

Rendón-Calle, Alejandra; Builes, Santiago; Calle‐Vallejo, Federico

doi:10.1016/j.apcatb.2020.119147

Cited by 64 publications

(98 citation statements)

References 72 publications

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“…Of course, more ingredients are needed for an accurate assessment of adsorption energies in solution, namely corrections to the adsorbed state [33,69] and solvation corrections [70–72] . In fact, recent studies coupling gas‐phase corrections and solvation corrections led to reaction free energies, equilibrium potentials and catalytic onset potentials in good agreement with experiments [32,73] …”

Section: Resultsmentioning

confidence: 86%

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Fast Correction of Errors in the DFT‐Calculated Energies of Gaseous Nitrogen‐Containing Species

2021

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Modeling adsorption phenomena on surfaces by DFT calculations often involves substantial errors, resulting in inaccurate predictions of catalytic activities. Such errors partly stem from the inaccurate description of the energetics of free molecules. Herein, we use a semiempirical group-additivity method to correct the DFT-calculated heats of formation of 106 carbonand nitrogen-containing gaseous compounds belonging to 15 different chemical families. PBE, PW91, RPBE and BEEF-vdW initially yield mean absolute errors (MAEs) with respect to experiments in the range of 0.32-0.75 eV. After correcting the systematic errors, the overall MAEs decrease to~0.05 eV. Additionally, upon applying the corrections to three types of reaction enthalpies, the resulting MAEs are below 0.10 eV. These functional-group corrections can be used in (electro)catalysis to correct the gas-phase references necessary to evaluate equilibrium potentials and adsorption energies, predict error cancellation, and assess conflicting experimental data.

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Section: Resultsmentioning

confidence: 86%

“…[70][71][72] In fact, recent studies coupling gasphase corrections and solvation corrections led to reaction free energies, equilibrium potentials and catalytic onset potentials in good agreement with experiments. [32,73]…”

Section: Brief Discussionmentioning

confidence: 99%

Fast Correction of Errors in the DFT‐Calculated Energies of Gaseous Nitrogen‐Containing Species

2021

Self Cite

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“…[12,34] Thus, we calculated the solvation energies by using an explicit solvation model, which contains three water molecules and is supposed to form a minimal hydrogen bond network of water molecules. [34] Though this limited model is not able to exactly account for the solvation effect, it is still a good compromise between efficiency and accuracy. [35] We calculated the solvation energy for each reaction species over the 1T'-MoS 2 catalyst.…”

Section: Computational Detailsmentioning

confidence: 99%

NO Electroreduction by Transition Metal Dichalcogenides with Chalcogen Vacancies

Tursun

2021

ChemElectroChem

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Nitric oxide electroreduction reaction (NOER) is one of the most attractive routes for ammonia synthesis and NOx‐related pollutant treatment. However, current research on NOER catalysts mainly focus on noble metals and single atom catalysts, while low‐cost transition metal dichalcogenides (TMDs) are rarely considered, let alone their product selectivity. Herein, using first‐principles calculations, we systematically investigate the performance of a series of single‐layer TMDs (MoS2, MoSe2, MoTe2, TaTe2 and WTe2) in the 1T’ phase as electrocatalysts for NOER. Our results reveal that defective 1T’‐MoS2 and 1T’‐MoSe2 monolayers (with the most common sulphur and selenium vacancies, respectively) exhibit excellent activity for NOER as well as high selectivity for ammonia, which can be correspondingly yielded at 0 and −0.06 V potentials, comparable to the best Pt‐based and single atom catalysts. Furthermore, these two catalysts efficiently suppress the competing hydrogen evolution reaction (HER). Thus, single‐layer TMDs synthesized with chalcogen vacancies may serve as efficient catalysts for electrochemical ammonia synthesis from pollutants and electrocatalytic denitrification.

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“…Additionally, TERS imaging visualizes the coadsorption competition over time and discerns pure pCTP nanodomains and binary nanodomains formed in the mixed SAMs, with a domain size down to <10 nm. Combined with density functional theory (DFT) calculations, we found that solvation effects can alter the thiolate adsorption energies on Au(111), [31][32][33] and thus pCTP would gradually replace pATP on the surface during the coadsorption time. Our findings indicate that TERS appears to be an attractive method for studying binary SAMs on atomically flat surfaces at the nanometer scale and molecular level under ambient conditions.…”

Section: Introductionmentioning

confidence: 98%

Nanoscale Chemical Imaging of Coadsorbed Thiolate Self-assembled Monolayers on Au(111) by Tip-Enhanced Raman Spectroscopy

Shao

Zheng

Lan

et al. 2022

Preprint

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Self-assembled monolayers (SAMs) of thiolates on metal surfaces are of key importance for engineering surfaces with tunable properties. However, it remains challenging to understand binary thiolate SAMs on metals at the nanoscale under ambient conditions. Here we employ tip-enhanced Raman spectroscopy (TERS) and density functional theory (DFT) calculations to investigate local information of binary SAMs on Au(111) coadsorbed from an equimolar mixture of p-cyanobenzenethiol (pCTP) and p-aminothiophenol (pATP), including chemical composition, coadsorption behavior, phase segregation, plasmon-induced photocatalysis, and solvation effects. We found that upon competitive adsorption of pCTP and pATP on Au(111) from a methanolic solution, the coadsorption initially occurs randomly and homogeneously; eventually, pATP is replaced by pCTP through gradual growth of pCTP nanodomains. TERS imaging also allows for visualization of the plasmon-induced coupling of pATP to p,p’-dimercaptoazobenzene (DMAB) and the solvation-induced phase segregation of the binary SAMs into nanodomains, with a spatial resolution of ~9 nm under ambient conditions. According to DFT calculations, these aromatic thiolates differing only in their functional groups, -CN versus –NH2, show different adsorption energy on Au(111) in vacuum and methanol, and thus the solvation effect on adsorption energy of these thiolates in methanol can determine the dispersion state and replacement order of the binary thiolates on Au(111).

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Substantial improvement of electrocatalytic predictions by systematic assessment of solvent effects on adsorption energies

Cited by 64 publications

References 72 publications

Fast Correction of Errors in the DFT‐Calculated Energies of Gaseous Nitrogen‐Containing Species

Fast Correction of Errors in the DFT‐Calculated Energies of Gaseous Nitrogen‐Containing Species

NO Electroreduction by Transition Metal Dichalcogenides with Chalcogen Vacancies

Nanoscale Chemical Imaging of Coadsorbed Thiolate Self-assembled Monolayers on Au(111) by Tip-Enhanced Raman Spectroscopy

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