Photoelectron Spectra of Aqueous Solutions from First Principles

Gaiduk, Alex P.; Govoni, Marco; Seidel, Robert; Skone, Jonathan H.; Winter, Bernd; Galli, Giulia

doi:10.1021/jacs.6b00225

Cited by 71 publications

(108 citation statements)

References 48 publications

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“…Overall, these results indicate that RSH and sc-hybrid functionals provide an accurate and robust description of the electronic properties of liquid water and the NO 3 − ion within a DFT framework while requiring a much lower computational cost than G 0 W 0 calculations. This conclusion is consistent with a previous study of aqueous solutions with simple ions, that is, Na + and Cl − ( 26 ). …”

Section: Resultssupporting

confidence: 94%

Electronic structure of aqueous solutions: Bridging the gap between theory and experiments

et al. 2017

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Section: Resultssupporting

confidence: 94%

Electronic structure of aqueous solutions: Bridging the gap between theory and experiments

et al. 2017

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“…After the dip and pull procedure, the intensity of this component is enhanced. Under such conditions, a second spectral fingerprint, near 17.8 eV, is observed and can be assigned to photoemission from the 1b 2 molecular orbital of liquid water (60). Analysis of VB spectra obtained under pristine and hydrated conditions confirms the presence of both Co 2+ and Co 3+ , centered at 2.1 eV and 1.2 eV below the Fermi level, respectively.…”

Section: Operando Spectroscopic Investigation Of the Biphasic Coo X Smentioning

confidence: 80%

“…The second region, between 3 and 7 eV below the Fermi level, is generated mainly by hybridization of O 2p orbitals, forming a relatively broad electronic band. Finally, beyond 8 eV below the Fermi level, hybridizations between O 2p valence orbitals from adsorbed and multilayer water on the WE surface contribute to the spectral intensity (58,59,60). The broad band at ~10.1 eV below the Fermi level arises from photoemission of the 1b 1 molecular orbital of water (58,59).…”

Section: Operando Spectroscopic Investigation Of the Biphasic Coo X Smentioning

confidence: 99%

Understanding the Oxygen Evolution Reaction Mechanism on CoO_x using Operando Ambient-Pressure X-ray Photoelectron Spectroscopy

et al. 2017

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ABSTRACT:Photoelectrochemical water splitting is a promising approach for renewable production of hydrogen from solar energy and requires interfacing advanced water splitting catalysts with semiconductors. Understanding the mechanism of function of such electrocatalysts at the atomic scale and under realistic working conditions is a challenging, yet important, task for advancing efficient and stable function. This is particularly true for the case of oxygen evolution catalysts and, here, we study a highly active Co 3 O 4 /Co(OH) 2 biphasic electrocatalyst on Si by means of operando ambient pressure X-ray photoelectron spectroscopy performed at the solid/liquid electrified interface. Spectral simulation and multiplet fitting reveal that the catalyst undergoes chemical-structural transformations as a function of the applied anodic potential, with complete conversion of the Co(OH) 2 and partial conversion of the spinel Co 3 O 4 phases to CoO(OH) under pre-catalytic electrochemical conditions. Furthermore, we observe new spectral features in both Co 2p and O 1s core level regions to emerge under oxygen evolution reaction conditions on CoO(OH). The operando photoelectron spectra support assignment of these newly observed features to highly active Co 4+ centers under catalytic conditions. Comparison of these results to those from a pure phase spinel Co 3 O 4 catalyst supports this interpretation and reveals that the presence of Co(OH) 2 enhances catalytic activity by promoting transformations to CoO(OH). The direct investigation of electrified interfaces presented in this work can be extended to different materials under realistic catalytic conditions, thereby providing a powerful tool for mechanism discovery and an enabling capability for catalyst design. Introduction Sustainable solutions are required to mitigate the impact of increasing world energy demand on the environment and avoid depletion of natural energy sources (1). While transduction of solar energy to electricity has already made a significant impact on the renewable energy sector, the intermittent nature of sunlight imposes critical storage challenges (2,3,4,5,6). Furthermore, addressing broader energy needs, particularly in transportation, requires new technologies for the next generation of renewable fuels. Within this context, (photo)electrochemical conversion of sunlight to hydrogen -or other chemical fuels -represents an appealing approach to both solar energy conversion and high energy density storage. An essential step in such artificial photosystems is the oxygen evolution reaction (OER), in which the protons and electrons required for the fuel formation reaction are harnessed from water (2-7, 8, 9). However, OER pathways can be complex and impose significant kinetic bottlenecks. To address this challenge, increasing efforts have been devoted to developing OER catalysts possessing high activity, long-term durability, and low cost, a combination of attributes that is most commonly obtained with first row transition metal oxides (10,11,12,13,14,15...

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“…This has been pursued by Koller et al [34] using a Yukawa screened hybrid functional, and by Skone et al [35], Ferrari et al [36], and Gerosa et al [37] in the form of global hybrid functionals. The resulting dielectric-dependent hybrid (DDH) functionals, primarily the global ones where α = ε −1 ∞ , have since been used to describe defects [38][39][40][41][42], band alignments of semiconductors [17], and electronic structures of aqueous solutions [43,44].…”

Section: Introductionmentioning

confidence: 99%

Nonempirical dielectric-dependent hybrid functional with range separation for semiconductors and insulators

Chen

Miceli

Rignanese

et al. 2018

Phys. Rev. Materials

142

148

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We present a general scheme of range-separated hybrid functionals in which the mixing parameters of Fock exchange are fully nonempirical and determined solely from the dielectric function.We showthat the full dielectric dependence leads to an unscreened Fock exchange in the short range, while in the long range the Fock exchange is correctly screened by the macroscopic dielectric constant. The range separation is obtained by fitting to the calculated static dielectric function in the long-wavelength limit. The resulting hybrid functional accurately accounts for electronic and structural properties of various semiconductors and insulators spanning a wide range of band gaps. We present a general scheme of range-separated hybrid functionals in which the mixing parameters of Fock exchange are fully nonempirical and determined solely from the dielectric function. We show that the full dielectric dependence leads to an unscreened Fock exchange in the short range, while in the long range the Fock exchange is correctly screened by the macroscopic dielectric constant. The range separation is obtained by fitting to the calculated static dielectric function in the long-wavelength limit. The resulting hybrid functional accurately accounts for electronic and structural properties of various semiconductors and insulators spanning a wide range of band gaps.

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Photoelectron Spectra of Aqueous Solutions from First Principles

Cited by 71 publications

References 48 publications

Electronic structure of aqueous solutions: Bridging the gap between theory and experiments

Electronic structure of aqueous solutions: Bridging the gap between theory and experiments

Understanding the Oxygen Evolution Reaction Mechanism on CoO_x using Operando Ambient-Pressure X-ray Photoelectron Spectroscopy

Nonempirical dielectric-dependent hybrid functional with range separation for semiconductors and insulators

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Photoelectron Spectra of Aqueous Solutions from First Principles

Cited by 71 publications

References 48 publications

Electronic structure of aqueous solutions: Bridging the gap between theory and experiments

Electronic structure of aqueous solutions: Bridging the gap between theory and experiments

Understanding the Oxygen Evolution Reaction Mechanism on CoOx using Operando Ambient-Pressure X-ray Photoelectron Spectroscopy

Nonempirical dielectric-dependent hybrid functional with range separation for semiconductors and insulators

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Understanding the Oxygen Evolution Reaction Mechanism on CoO_x using Operando Ambient-Pressure X-ray Photoelectron Spectroscopy