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We have used molecular simulation and methods of importance sampling to study the thermodynamics and kinetics of ionic charge separation at a liquid water-metal interface. We have considered this process using canonical examples of two different classes of ions: a simple alkali-halide pair, Na+I-, or classical ions, and the products of water autoionization, H3O+OH-, or water ions. We find that for both ion classes, the microscopic mechanism of charge separation, including water's collective role in the process, is conserved between the bulk liquid and the electrode interface. However, the thermodynamic and kinetic details of the process differ between these two environments in a way that depends on ion type. In the case of the classical ion pairs, a higher free-energy barrier to charge separation and a smaller flux over that barrier at the interface result in a rate of dissociation that is 40 times slower relative to the bulk. For water ions, a slightly higher free-energy barrier is offset by a higher flux over the barrier from longer lived hydrogen-bonding patterns at the interface, resulting in a rate of association that is similar both at and away from the interface. We find that these differences in rates and stabilities of charge separation are due to the altered ability of water to solvate and reorganize in the vicinity of the metal interface.

We have used molecular simulation and methods of importance sampling to study the thermodynamics and kinetics of ionic charge separation at a liquid water-metal interface. We have considered this process using canonical examples of two different classes of ions: a simple alkali-halide pair, Na+I-, or classical ions and the products of water autoionization, H3O+OH-, or water ions. We find that for both ion classes, the microscopic mechanism of charge separation, including water's collective role in the process, is conserved between the bulk liquid and the electrode interface. However, the thermodynamic and kinetic details of the process differ between these two environments in a way that depends on ion type. In the case of the classical ion pairs, a higher free-energy barrier to charge separation and a smaller flux over that barrier at the interface result in a rate of dissociation that is 40 times slower relative to the bulk. For water ions, a slightly higher free-energy barrier is offset by a higher flux over the barrier from longer lived hydrogen-bonding patterns at the interface, resulting in a rate of association that is similar both at and away from the interface.We find that these differences in rates and stabilities of charge separation are due to the altered ability of water to solvate and reorganize in the vicinity of the metal interface. [ABSTRACT FROM AUTHOR]

The high overpotential in water oxidation on anodes is a limiting factor for the large‐scale application of photoelectrochemical cells. To overcome this limitation, it is essential to understand the four proton‐coupled electron transfer (PCET) steps in the reaction mechanism and their implications to the overpotential. Herein, a simple scheme to compute the energies of the PCET steps in water oxidation on the aqueous TiO2 surface using a hybrid density functional is described. An energy level diagram for fully decoupled electron‐ and proton‐transfer reactions in which both electronic and protonic levels are placed on the same potential scale is also described. The level diagram helps to visualize the electronic and protonic components of the overpotential, and points out what are needed to improve. For TiO2, it is found that its catalytic activity is due to aligning the protonic energy levels in the PCET steps, while improving the activity requires also aligning the electronic levels. [ABSTRACT FROM AUTHOR]

The high overpotential in water oxidation on anodes is a limiting factor for the large-scale application of photoelectrochemical cells. To overcome this limitation, it is essential to understand the four proton-coupled electron transfer (PCET) steps in the reaction mechanism and their implications to the overpotential. Herein, a simple scheme to compute the energies of the PCET steps in water oxidation on the aqueous TiO2 surface using a hybrid density functional is described. An energy level diagram for fully decoupled electron- and proton-transfer reactions in which both electronic and protonic levels are placed on the same potential scale is also described. The level diagram helps to visualize the electronic and protonic components of the overpotential, and points out what are needed to improve. For TiO2, it is found that its catalytic activity is due to aligning the protonic energy levels in the PCET steps, while improving the activity requires also aligning the electronic levels. [ABSTRACT FROM AUTHOR]

The high overpotential in water oxidation on anodes is a limiting factor for the large‐scale application of photoelectrochemical cells. To overcome this limitation, it is essential to understand the four proton‐coupled electron transfer (PCET) steps in the reaction mechanism and their implications to the overpotential. Herein, a simple scheme to compute the energies of the PCET steps in water oxidation on the aqueous TiO2 surface using a hybrid density functional is described. An energy level diagram for fully decoupled electron‐ and proton‐transfer reactions in which both electronic and protonic levels are placed on the same potential scale is also described. The level diagram helps to visualize the electronic and protonic components of the overpotential, and points out what are needed to improve. For TiO2, it is found that its catalytic activity is due to aligning the protonic energy levels in the PCET steps, while improving the activity requires also aligning the electronic levels. Scheming: A scheme for computing the thermochemistry of proton‐coupled electron transfer (PCET) reactions at interfaces is described. In analogy with electronic energy levels, an appealing concept of protonic energy levels is proposed to visualize the thermodynamics of PCET in a level diagram. This diagram helps to elucidate the electronic and protonic components of thermodynamic overpotentials in photocatalysis. [ABSTRACT FROM AUTHOR]

The high overpotential in water oxidation on anodes is a limiting factor for the large ‐ scale application of photoelectrochemical cells. To overcome this limitation, it is essential to understand the four proton ‐ coupled electron transfer (PCET) steps in the reaction mechanism and their implications to the overpotential. Herein, a simple scheme to compute the energies of the PCET steps in water oxidation on the aqueous TiO2 surface using a hybrid density functional is described. An energy level diagram for fully decoupled electron ‐ and proton ‐ transfer reactions in which both electronic and protonic levels are placed on the same potential scale is also described. The level diagram helps to visualize the electronic and protonic components of the overpotential, and points out what are needed to improve. For TiO2, it is found that its catalytic activity is due to aligning the protonic energy levels in the PCET steps, while improving the activity requires also aligning the electronic levels. Bei der Berechnung der Thermochemie des protongekoppelten Elektronentransfers (PCET) an Grenzflächen können analog zu elektronischen Energieniveaus auch protonische Energieniveaus genutzt werden, um die PCET ‐ Thermodynamik zu beschreiben. Die resultierenden Diagramme veranschaulichen die elektronischen und protonischen Beiträge zu thermodynamischen Überpotentialen in der Photokatalyse. [ABSTRACT FROM AUTHOR]

The high overpotential in water oxidation on anodes is a limiting factor for the large-scale application of photoelectrochemical cells. To overcome this limitation, it is essential to understand the four proton-coupled electron transfer (PCET) steps in the reaction mechanism and their implications to the overpotential. Herein, a simple scheme to compute the energies of the PCET steps in water oxidation on the aqueous TiO2 surface using a hybrid density functional is described. An energy level diagram for fully decoupled electron- and proton-transfer reactions in which both electronic and protonic levels are placed on the same potential scale is also described. The level diagram helps to visualize the electronic and protonic components of the overpotential, and points out what are needed to improve. For TiO2, it is found that its catalytic activity is due to aligning the protonic energy levels in the PCET steps, while improving the activity requires also aligning the electronic levels. [ABSTRACT FROM AUTHOR]

The high overpotential in water oxidation on anodes is a limiting factor for the large‐scale application of photoelectrochemical cells. To overcome this limitation, it is essential to understand the four proton‐coupled electron transfer (PCET) steps in the reaction mechanism and their implications to the overpotential. Herein, a simple scheme to compute the energies of the PCET steps in water oxidation on the aqueous TiO2 surface using a hybrid density functional is described. An energy level diagram for fully decoupled electron‐ and proton‐transfer reactions in which both electronic and protonic levels are placed on the same potential scale is also described. The level diagram helps to visualize the electronic and protonic components of the overpotential, and points out what are needed to improve. For TiO2, it is found that its catalytic activity is due to aligning the protonic energy levels in the PCET steps, while improving the activity requires also aligning the electronic levels. [ABSTRACT FROM AUTHOR]

The high overpotential in water oxidation on anodes is a limiting factor for the large ‐ scale application of photoelectrochemical cells. To overcome this limitation, it is essential to understand the four proton ‐ coupled electron transfer (PCET) steps in the reaction mechanism and their implications to the overpotential. Herein, a simple scheme to compute the energies of the PCET steps in water oxidation on the aqueous TiO2 surface using a hybrid density functional is described. An energy level diagram for fully decoupled electron ‐ and proton ‐ transfer reactions in which both electronic and protonic levels are placed on the same potential scale is also described. The level diagram helps to visualize the electronic and protonic components of the overpotential, and points out what are needed to improve. For TiO2, it is found that its catalytic activity is due to aligning the protonic energy levels in the PCET steps, while improving the activity requires also aligning the electronic levels. Bei der Berechnung der Thermochemie des protongekoppelten Elektronentransfers (PCET) an Grenzflächen können analog zu elektronischen Energieniveaus auch protonische Energieniveaus genutzt werden, um die PCET ‐ Thermodynamik zu beschreiben. Die resultierenden Diagramme veranschaulichen die elektronischen und protonischen Beiträge zu thermodynamischen Überpotentialen in der Photokatalyse. [ABSTRACT FROM AUTHOR]

The high overpotential in water oxidation on anodes is a limiting factor for the large‐scale application of photoelectrochemical cells. To overcome this limitation, it is essential to understand the four proton‐coupled electron transfer (PCET) steps in the reaction mechanism and their implications to the overpotential. Herein, a simple scheme to compute the energies of the PCET steps in water oxidation on the aqueous TiO2 surface using a hybrid density functional is described. An energy level diagram for fully decoupled electron‐ and proton‐transfer reactions in which both electronic and protonic levels are placed on the same potential scale is also described. The level diagram helps to visualize the electronic and protonic components of the overpotential, and points out what are needed to improve. For TiO2, it is found that its catalytic activity is due to aligning the protonic energy levels in the PCET steps, while improving the activity requires also aligning the electronic levels. Scheming: A scheme for computing the thermochemistry of proton‐coupled electron transfer (PCET) reactions at interfaces is described. In analogy with electronic energy levels, an appealing concept of protonic energy levels is proposed to visualize the thermodynamics of PCET in a level diagram. This diagram helps to elucidate the electronic and protonic components of thermodynamic overpotentials in photocatalysis. [ABSTRACT FROM AUTHOR]

Disordered nanoporous and "hard" carbons are widely used in batteries and supercapacitors, but their atomic structures are poorly determined. Here, we combine machine learning and DFT to obtain new atomistic insight into carbonaceous energy materials. We study structural models of porous and graphitic carbons, and Na intercalation as relevant for sodium-ion batteries.