Kinetic origins of the metastable zone width in the manganese oxide Pourbaix diagram

The metastable zone width is the region on a phase diagram where a phase transformation is thermodynamically favored but kinetically hindered. Reaction conditions may need to be far beyond the Pourbaix phase diagram boundaries to initiate nucleation.

High zT in Electrodeposited Silver Selenide Films: From Pourbaix Diagram to a Flexible Thermoelectric Module

In the last years, to explore new thermoelectric materials with low-toxicity, earth-abundant, and high-efficiency has become essential. Following this trend, sustainable, easily scalable, and cost-effective fabrication methods, such as electrochemical...

Predicting aqueous stability of solid with computed Pourbaix diagram using SCAN functional

In this work, using the SCAN functional, we develop a simple method on top of the Materials Project (MP) Pourbaix diagram framework to accurately predict the aqueous stability of solids. We extensively evaluate the SCAN functional’s performance in computed formation enthalpies for a broad range of oxides and develop Hubbard U corrections for transition-metal oxides where the standard SCAN functional exhibits large deviations. The performance of the calculated Pourbaix diagram using the SCAN functional is validated with comparison to the experimental and the MP PBE Pourbaix diagrams for representative examples. Benchmarks indicate the SCAN Pourbaix diagram systematically outperforms the MP PBE in aqueous stability prediction. We further show applications of this method in accurately predicting the dissolution potentials of the state-of-the-art catalysts for oxygen evolution reaction in acidic media.

Predicting Aqueous Stability of Solid with Computed Pourbaix Diagram using SCAN Functional

In this work, using the SCAN functional, we develop a simple method on top of the Materials Project (MP) Pourbaix diagram framework to accurately predict the aqueous stability of solids. We extensively evaluate the SCAN functional’s performance in computed formation enthalpies for a broad range of oxides and develop Hubbard U corrections for transition metal oxides where the standard SCAN functional exhibits large deviations. The performance of the calculated Pourbaix diagram using the SCAN functional is validated with comparison to the experimental and the MP PBE Pourbaix diagrams for representative examples. Benchmarks indicate the SCAN Pourbaix diagram systematically outperforms the MP PBE in aqueous stability prediction. We further show applications of this method in accurately predicting the dissolution potentials of the state-of-the-art catalysts for oxygen evolution reaction in acidic media.

Predicting Aqueous Stability of Solid with Computed Pourbaix Diagram using SCAN Functional

In this work, using the SCAN functional, we develop a simple method on top of the Materials Project (MP) Pourbaix diagram framework to accurately predict the aqueous stability of solids. We extensively evaluate the SCAN functional’s performance in computed formation enthalpies for a broad range of oxides and develop Hubbard U corrections for transition metal oxides where the standard SCAN functional exhibits large deviations. The performance of the calculated Pourbaix diagram using the SCAN functional is validated with comparison to the experimental and the MP PBE Pourbaix diagrams for representative examples. Benchmarks indicate the SCAN Pourbaix diagram systematically outperforms the MP PBE in aqueous stability prediction. We further show applications of this method in accurately predicting the dissolution potentials of the state-of-the-art catalysts for oxygen evolution reaction in acidic media.

[CoII(BPyPy2COH)(OH2)2]2+: A Catalytic Pourbaix Diagram and AIMD Simulations on Four Key Intermediates

Proton reduction by [CoII(BPyPy2COH)(OH2)2]2+ (BPyPy2COH = [2,2'-bipyridin]-6-yl-di[pyridin-2-yl]methanol) proceeds through two distinct, pH-dependent pathways involving proton-coupled electron transfer (PCET), reduction and protonation steps. In this account we give an overview of the key mechanistic aspects in aqueous solution from pH 3 to 10, based on electrochemical data, time-resolved spectroscopy and ab initio molecular dynamics simulations of the key catalytic intermediates. In the acidic pH branch, a PCET to give a CoIII hydride is followed by a reduction and a protonation step, to close the catalytic cycle. At elevated pH, a reduction to CoI is observed, followed by a PCET to a CoII hydride, and the catalytic cycle is closed by a slow protonation step. In our simulation, both CoI and CoII–H feature a strong interaction with the surrounding solvent via hydrogen bonding, which is expected to foster the following catalytic step.