Manipulating Intermetallic Charge Transfer for Switchable External Stimulus-Enhanced Water Oxidation Electrocatalysis.

Electrocatalytic processes involving the oxygen evolution reaction (OER) present a kinetic bottleneck due to the existence of linear-scaling relationships, which bind the energies of the different intermediates in the mechanism limiting optimization. Here, we offer a way to break these scaling relationships and enhance the electrocatalytic activity of a Co-Fe Prussian blue modified electrode in OER by applying external stimuli. Improvements of ≈11 % and ≈57 % were achieved under magnetic field (0.2 T) and light irradiation (100 mW cm-2 ), respectively, when working at fixed overpotential, η=0.6 V at pH 7. The observed enhancements strongly tie in with the intermetallic charge transfer (IMCT) intensity between Fe and Co sites. Density Functional Theory simulations suggest that tuning the IMCT can lead to a change of the OER mechanism to an external stimuli-sensitive spin crossover-based pathway, which opens the way for switchable electrocatalytic devices.

Lowering the Water Oxidation Overpotential by Spin-Crossover in Cobalt Hexacyanoferrate.

The oxygen evolution reaction (OER) is limited by the inherent linear scaling relationships of its reaction intermediates. Manipulating the spin configuration of the water oxidation intermediates allows us to overcome these constraints. Cobalt hexacyanoferrate (CoFe-PB) is an efficient and robust water oxidation catalyst and further known as a magnetic switch. Its versatile electronic structure renders it a potential candidate for magnetic tuning of the OER. Herein, we used first-principles density functional theory calculations to describe the OER on two different CoFe-PB model systems and evaluated the possibility for spin-crossover (SCO) of their resting states. We show that SCO during OER can significantly lower the overpotential by 0.7 V, leading to an overpotential of around 0.3 V, which is in agreement with the experimentally measured value. Applying an external potential >1.5 V vs SHE, the SCO-assisted pathway becomes largely favored and most likely the predominant reaction pathway.

Quasi-degenerate states and their dynamics in oxygen deficient reducible metal oxides.

The physical and chemical properties of oxides are defined by the presence of oxygen vacancies. Experimentally, non-defective structures are almost impossible to achieve due to synthetic constraints. Therefore, it is crucial to account for vacancies when evaluating the characteristics of these materials. The electronic structure of oxygen-depleted oxides deeply differs from that of the native forms, in particular, of reducible metal oxides, where excess electrons can localize in various distinct positions. In this perspective, we present recent developments from our group describing the complexity of these defective materials that highlight the need for an accurate description of (i) intrinsic vacancies in polar terminations, (ii) multiple geometries and complex electronic structures with several states attainable at typical working conditions, and (iii) the associated dynamics for both vacancy diffusion and the coexistence of more than one electronic structure. All these aspects widen our current understanding of defects in oxides and need to be adequately introduced in emerging high-throughput screening methodologies.

Versatile Nature of Oxygen Vacancies in Bismuth Vanadate Bulk and (001) Surface.

Bismuth vanadate (BiVO4) has emerged as one of the most promising photoanode materials for solar fuel production. Oxygen vacancies play a pivotal role in the photoelectrochemical efficiency, yet their electronic nature and contribution to  n-type conductivity are still under debate. Using first-principles calculations, we show that oxygen vacancies in BiVO4 have two distinguishable geometric configurations characterized by either undercoordinated, reduced VIVO3 and BiIIO7 subunits or a VIV-O-VIV/V bridge (split vacancy), quenching the oxygen vacancy site. While both configurations have similar energies in the bulk, the (001) subsurface acts like an energetic sink that stabilizes the split oxygen vacancy by ∼1 eV. The barrierless creation of a bridging V2O7 unit allows for partial electron delocalization throughout the near-surface region, consistent with recent experimental observations indicating that BiVO4(001) is an electron-rich surface.

Level Alignment as Descriptor for Semiconductor/Catalyst Systems in Water Splitting: The Case of Hematite/Cobalt Hexacyanoferrate Photoanodes.

The realization of artificial photosynthesis may depend on the efficient integration of photoactive semiconductors and catalysts to promote photoelectrochemical water splitting. Many efforts are currently devoted to the processing of multicomponent anodes and cathodes in the search for appropriate synergy between light absorbers and active catalysts. No single material appears to combine both features. Many experimental parameters are key to achieve the needed synergy between both systems, without clear protocols for success. Herein, we show how computational chemistry can shed some light on this cumbersome problem. DFT calculations are useful to predict adequate energy-level alignment for thermodynamically favored hole transfer. As proof of concept, we experimentally confirmed the limited performance enhancement in hematite photoanodes decorated with cobalt hexacyanoferrate as a competent water-oxidation catalyst. Computational methods describe the misalignment of their energy levels, which is the origin of this mismatch. Photoelectrochemical studies indicate that the catalyst exclusively shifts the hematite surface state to lower potentials, which therefore reduces the onset for water oxidation. Although kinetics will still depend on interface architecture, our simple theoretical approach may identify and predict plausible semiconductor/catalyst combinations, which will speed up experimental work towards promising photoelectrocatalytic systems.

Cobalt Hexacyanoferrate on BiVO4 Photoanodes for Robust Water Splitting.

The efficient integration of photoactive and catalytic materials is key to promoting photoelectrochemical water splitting as a sustainable energy technology built on solar power. Here, we report highly stable water splitting photoanodes from BiVO4 photoactive cores decorated with CoFe Prussian blue-type electrocatalysts (CoFe-PB). This combination decreases the onset potential of BiVO4 by ∼0.8 V (down to 0.3 V vs reversible hydrogen electrode (RHE)) and increases the photovoltage by 0.45 V. The presence of the catalyst also leads to a remarkable 6-fold enhancement of the photocurrent at 1.23 V versus RHE, while keeping the light-harvesting ability of BiVO4. Structural and mechanistic studies indicate that CoFe-PB effectively acts as a true catalyst on BiVO4. This mechanism, stemming from the adequate alignment of the energy levels, as showed by density functional theory calculations, allows CoFe-PB to outperform all previous catalyst/BiVO4 junctions and, in addition, leads to noteworthy long-term stability. A bare 10-15% decrease in photocurrent was observed after more than 50 h of operation under light irradiation.

A Database of the Structural and Electronic Properties of Prussian Blue, Prussian White, and Berlin Green Compounds through Density Functional Theory.

Prussian blue and its related compounds are formed by cheap and abundant metals and have shown their importance in the generation of new fuels by renewable sources. To optimize these compounds it is important to understand their electronic structure and thus establish robust structure-activity relationships. To this end, we employed theoretical simulations based on density functional theory, employing functionals of different degree of complexity, including pure generalized gradient approximation (GGA) and GGA+U functionals, which introduce self-interaction correction terms through the Hubbard parameter, and compared those to the hybrid functionals HSE03 and HSE06. With this robust setup, we can identify an appropriate computational scheme that provides the best compromise between computational demand and accuracy. A complete database considering Berlin green and Prussian blue and white for all alkaline cations is presented.