Relating 3D Geometry and Photoelectrochemical Activity of WO3-loaded n-Si Nanowires: Design Rules for Photoelectrodes

Nanostructured electrodes for photoelectrochemical (PEC) applications, such as water splitting, have rather low photocurrent density regarding their highly enlarged surface area compared to plain electrodes. This demands for further understanding of the relation between the 3D geometry and the PEC activity. To this end, we fabricate WO3/Si nanowire array photoanodes with various nanowire lengths (1.3 µm, 2.7 µm, 3.2 µm and 3.8 µm) and different WO3 thicknesses (10 nm, 30 nm and 50 nm) using wet chemical etching for nanostructuring of Si and atomic layer deposition for the deposition of WO3. It is found that by increasing the etching time, the nanowires become longer and the top surface area decreases. The photocurrent density first increases and then decreases with increasing Si etching time. This behaviour can be explained by different and opposite effects regarding absorption, geometry and materials specific properties. Particularly, the decrease of the photocurrent density can be due to: First, the longer the nanowires the heavier the recombination of the photogenerated carriers. Second, the long-time Si etching results in a loss of top part of the nanowire arrays. Because of shadowing, the WO3 located at the top part of the nanowires is more effective than that at the bottom part for the WO3/Si nanowire arrays and therefore the photocurrent is decreased. It reveals a trade-off between the top part surface area and the length of the nanowires. This study contributes to a better understand of the relation between the geometry of nanostructures and the performance of PEC electrodes.</p

Monolayer Nitrides Doped with Transition Metals as Efficient Catalysts for Water Oxidation: The Singular Role of Nickel

Exploration of precious-metal-free catalysts for water splitting is of great importance in developing renewable energy conversion and storage technologies. In this paper, on the basis of density functional theory calculations, we reveal the link between the oxygen evolution reaction (OER) activities and the electronic properties of pure and first-row transition-metal (TM)-doped AlN and GaN two-dimensional monolayers. We find that Ni-doped layers are singularly appealing because they lead to a low overpotential (0.4 V). Early TM dopants are not suited for the OER because they bind the intermediate species OH or O too strongly, which leads to very large overpotentials, or no OER activity at all. The late TM dopants Cu and Zn show less or no OER activity as they bind the intermediate species too weakly. Although in many cases the overpotential can be traced back to an OOH intermediate species being adsorbed too weakly compared to an OH species, the Ni dopant breaks this rule by stabilizing the OOH adsorbant. The stabilization can be correlated with a switch from a high-spin to a low-spin state of the dopant atom. This ability to change spin states offers an exciting ingredient for the design of OER catalysts.</p

Tailoring the performance of ZnO for oxygen evolution by effective transition metal doping

In the quest for active and inexpensive (photo)electrocatalysts, atomistic simulations of the oxygen evolution reaction (OER) are essential for understanding the catalytic process of water splitting at solid surfaces. In this paper, we study the enhancement of the OER by first-row transition-metal (TM) doping of the abundant semiconductor ZnO, using density functional theory (DFT) calculations on a substantial number of possible structures and bonding geometries. The calculated overpotential for undoped ZnO is 1.0 V. For TM dopants in the 3d series from Mn to Ni, the overpotentials decrease from 0.9 V for Mn, and 0.6 V for Fe, down to 0.4 V for Co, and rise again to 0.5 V for Ni and 0.8 eV for Cu. We analyze the overpotentials in terms of the binding to the surface of the species involved in the four reaction steps of the OER. The Gibbs free energies associated with the adsorption of these intermediate species increase down the series from Mn to Zn, but the difference between OH and OOH adsorption (the species involved in the first, respectively the third reaction step) is always in the range 3.0-3.3 eV, despite a considerable variation in possible bonding geometries. The bonding of the O intermediate species (involved in the second reaction step), which is optimal for Co, and to a somewhat lesser extend for Ni, then ultimately determines the overpotential. These results imply that both Co and Ni are promising dopants for increasing the activity of ZnO-based anodes for the OER.</p

Modeling and Simulations in Photoelectrochemical Water Oxidation: From Single Level to Multiscale Modeling

This review summarizes recent developments, challenges, and strategies in the field of modeling and simulations of photoelectrochemical (PEC) water oxidation. We focus on water splitting by metal-oxide semiconductors and discuss topics such as theoretical calculations of light absorption, band gap/band edge, charge transport, and electrochemical reactions at the electrode–electrolyte interface. In particular, we review the mechanisms of the oxygen evolution reaction, strategies to lower overpotential, and computational methods applied to PEC systems with particular focus on multiscale modeling. The current challenges in modeling PEC interfaces and their processes are summarized. At the end, we propose a new multiscale modeling approach to simulate the PEC interface under conditions most similar to those of experiments. This approach will contribute to identifying the limitations at PEC interfaces. Its generic nature allows its application to a number of electrochemical systems.</p

Robert B. Vance v. Paul V. Fordham : Appellant\u27s Reply Brief

Appeal from the Judgment of the Third Judicial District Court for Salt Lake County. Honorable Christine M. Durham, Judge affirming the order of the Department of Registration

Understanding the Impact of Different Types of Surface States on Photoelectrochemical Water Oxidation: A Microkinetic Modeling Approach

The oxygen evolution reaction (OER) has been identified as one of the performance-limiting processes in solar water splitting using photoelectrochemical (PEC) cells. One of the reasons for the low OER performance is related to the existence of different types of surface states at the semiconductor–electrolyte interface: recombining surface states (r-SS) and surface states due to intermediate species (i-SS). Since the impact of surface states on OER is still under debate, we investigate how different types of surface states affect PEC water oxidation and how they impact experimental measurements. In a new computational approach, we combine a microkinetic model of the OER on the semiconductor surface with the charge carrier dynamics within the semiconductor. The impact of r-SS and i-SS on the current–voltage curves, hole flux, surface state capacitance, Mott–Schottky plots, and chopped light measurements is systematically investigated. It is found that (a) r-SS results in a capacitance peak below the OER onset potential, while i-SS results in a capacitance peak around the onset potential; (b) r-SS leads to an increase in the OER onset potential and a decrease in the saturation current density; (c) r-SS leads to Fermi-level pinning before the onset potential, while i-SS does not result in Fermi-level pinning; and (d) a smaller capacitance peak of i-SS can be an indication of the lower catalytic performance of the semiconductor surface. Our approach in combination with experimental comparison allows distinguishing the impact of r-SS and i-SS in PEC experiments. We conclude that r-SS reduces the OER performance and i-SS mediates the OER.</p

Boosting the Performance of WO3/n‐Si Heterostructures for Photoelectrochemical Water Splitting: from the Role of Si to Interface Engineering

Metal oxide/Si heterostructures make up an exciting design route to high‐performance electrodes for photoelectrochemical (PEC) water splitting. By monochromatic light sources, contributions of the individual layers in WO3/n‐Si heterostructures are untangled. It shows that band bending near the WO3/n‐Si interface is instrumental in charge separation and transport, and in generating a photovoltage that drives the PEC process. A thin metal layer inserted at the WO3/n‐Si interface helps in establishing the relation among the band bending depth, the photovoltage, and the PEC activity. This discovery breaks with the dominant Z‐scheme design idea, which focuses on increasing the conductivity of an interface layer to facilitate charge transport, but ignores the potential profile around the interface. Based on the analysis, a high‐work‐function metal is predicted to provide the best interface layer in WO3/n‐Si heterojunctions. Indeed, the fabricated WO3/Pt/n‐Si photoelectrodes exhibit a 2 times higher photocurrent density at 1.23 V versus reversible hydrogen electrode (RHE) and a 10 times enhancement at 1.6 V versus RHE compared to WO3/n‐Si. Here, it is essential that the native SiO2 layer at the interface between Si and the metal is kept in order to prevent Fermi level pinning in the Schottky contact between the Si and the metal.</p

The Importance of Charge Redistribution during Electrochemical Reactions: A Density Functional Theory Study of Silver Orthophosphate (Ag3PO4)

The structural sensitivity of silver orthophosphate (Ag 3 PO 4 ) for photo-electrochemical water oxidation on (100), (110) and (111) surfaces has recently been reported by experimental studies (D. J. Martin et al., Energy Environ. Sci., 2013, 6, 3380-3386). The (111) surface showed the highest performance with an oxygen evolution rate of 10 times higher than the other surfaces. The high performance of the (111) surface was attributed to high hole mobility, high surface energy and, in a recent theoretical study (Z. Ma et al., RSC Adv., 2017, 7, 23994-24003), to a lower OH adsorption energy and the band structure. The investigations are based on a few structures and a full atomistic picture of the Ag 3 PO 4 under electrochemical reactions is still missing. Therefore, we report here a systematic study of the oxygen evolution reaction (OER) of Ag 3 PO 4 (100), (110), and (111) surfaces by density functional theory (DFT) calculations. Through a detailed investigation of the reaction energies and the overpotentials of OER on all possible surface orientations with all possible terminations and different involvement of Ag adsorption sites, we can confirm that (111) surfaces are highly active. However, surface orientation was not found to exclusively determine the electrochemical activity; neither did the number of Ag atoms involved in the adsorption of the intermediate species nor the type of surface termination or the different potential determining reaction steps. By using Bader charge analysis and investigation of the charge redistribution during OER, we found that the highest activity, i.e. lowest overpotential, is related to the charge redistribution of two OER steps, namely the O ad and the HOO ad formation. If the charge redistribution between these steps is small, then the overpotential is small and, hence, the activity is high. Charge redistributions are usually small for the (111) surface and therefore the (111) surface is usually the most active one. The concept of charge redistribution being decisive for the high activity of Ag 3 PO 4 may open a new design strategy for materials with highly efficient electrochemical surfaces.</p

From Geometry to Activity: A Quantitative Analysis of WO3/Si Micropillar Arrays for Photoelectrochemical Water Splitting

The photoelectrochemical (PEC) activity of microstructured electrodes remains low despite the highly enlarged surface area and enhanced light harvesting. To obtain a deeper understanding of the effect of 3D geometry on the PEC performance, well‐defined WO3/n‐Si and WO3/pn‐Si micropillar arrays are fabricated and subjected to a quantitative analysis of the relationship between the geometry of the micropillars (length, pitch) and their PEC activity. For WO3/n‐Si micropillars, it is found that the photocurrent increases for WO3/n‐Si pillars, but not in proportion to the increase in surface area that results from increased pillar length or reduced pillar pitch. Optical simulations show that a reduced pillar pitch results in areas of low light intensity due to a shadowing effect. For WO3/pn‐Si micropillar photoelectrodes, the p–n junction enhances the photocurrent density up to a factor of 4 at low applied bias potential (0.8 V vs RHE) compared to the WO3/n‐Si. However, the enhancement in photocurrent density increases first and then decreases with reduced pillar pitch, which scales with the photovoltage generated by the p–n junction. This is related to an increased dead layer of the p–n junction Si surface, which results in a decreased photovoltage even though the total surface area increases.</p

Enhanced electrochemical water oxidation: the impact of nanoclusters and nanocavities

The structures of transition metal surfaces and metal oxides are commonly believed to have a significant effect on the catalytic reactions. Density functional theory calculations are therefore used in this study to investigate the oxygen evolution reaction (OER) over nanostructured, i.e. nanocluster and nanocavity, surfaces of hematite (Fe2O3). The calculated results demonstrate an optimum nanocluster size with respect to the OER overpotential. The presence of nanoclusters on the electrode is regarded as an attractive strategy for increasing the activity in photoelectrochemical water splitting. However, in this work, we found that the presence of a nanocavity is a more effective strategy for lowering the overpotential compared to nanoclusters. This finding of the nanocavity-favoured OER for hematite surfaces is verified by similar simulations of WO3 surfaces.</p