Energy harvested directly from sunlight offers a desirable approach toward fulfilling, with minimal environmental impact, the need for clean energy. Solar energy is a decentralized and inexhaustible natural resource, with the magnitude of the available solar power striking the earth’s surface at any one instant equal to 130 million 500 MW power plants.1 However, several important goals need to be met to fully utilize solar energy for the global energy demand. First, the means for solar energy conversion, storage, and distribution should be environmentally benign, i.e. protecting ecosystems instead of steadily weakening them. The next important goal is to provide a stable, constant energy flux. Due to the daily and seasonal variability in renewable energy sources such as sunlight, energy harvested from the sun needs to be efficiently converted into chemical fuel that can be stored, transported, and used upon demand. The biggest challenge is whether or not these goals can be met in a costeffective way on the terawatt scale.2

http://pubs.acs.org/doi/pdf/10.1021/cr1002326

Solar Water Splitting Cells

Objective evaluation of the activity of electrocatalysts for water oxidation is of fundamental importance for the development of promising energy conversion technologies including integrated solar water-splitting devices, water electrolyzers, and Li-air batteries. However, current methods employed to evaluate oxygen-evolving catalysts are not standardized, making it difficult to compare the activity and stability of these materials. We report a protocol for evaluating the activity, stability, and Faradaic efficiency of electrodeposited oxygen-evolving electrocatalysts. In particular, we focus on methods for determining electrochemically active surface area and measuring electrocatalytic activity and stability under conditions relevant to an integrated solar water-splitting device. Our primary figure of merit is the overpotential required to achieve a current density of 10 mA cm–2 per geometric area, approximately the current density expected for a 10% efficient solar-to-fuels conversion device. Utilizing ...

Benchmarking Heterogeneous Electrocatalysts for the Oxygen Evolution Reaction

Objective comparisons of electrocatalyst activity and stability using standard methods under identical conditions are necessary to evaluate the viability of existing electrocatalysts for integration into solar-fuel devices as well as to help inform the development of new catalytic systems. Herein, we use a standard protocol as a primary screen for evaluating the activity, short-term (2 h) stability, and electrochemically active surface area (ECSA) of 18 electrocatalysts for the hydrogen evolution reaction (HER) and 26 electrocatalysts for the oxygen evolution reaction (OER) under conditions relevant to an integrated solar water-splitting device in aqueous acidic or alkaline solution. Our primary figure of merit is the overpotential necessary to achieve a magnitude current density of 10 mA cm–2 per geometric area, the approximate current density expected for a 10% efficient solar-to-fuels conversion device under 1 sun illumination. The specific activity per ECSA of each material is also reported. Among HER...

Benchmarking Hydrogen Evolving Reaction and Oxygen Evolving Reaction Electrocatalysts for Solar Water Splitting Devices

1. Setting the Scope of the Challenge 6474 1.1. The Need for Solar Energy Supply and Storage 6474 1.2. An Imperative for Discovery Research 6477 1.3. Scope of Review 6478 2. Large-Scale Centralized Energy Storage 6478 2.1. Pumped Hydroelectric Energy Storage (PHES) 6479 2.2. Compressed Air Energy Storage (CAES) 6480 3. Smaller Scale Grid and Distributed Energy Storage 6481 3.1. Flywheel Energy Storage (FES) 6481 3.2. Superconducting Magnetic Energy Storage 6482 4. Chemical Energy Storage: Electrochemical 6482 4.1. Batteries 6482 4.1.1. Lead-Acid Batteries 6483 4.1.2. Alkaline Batteries 6484 4.1.3. Lithium-Ion Batteries 6484 4.1.4. High-Temperature Sodium Batteries 6484 4.1.5. Liquid Flow Batteries 6485 4.1.6. Metal-Air Batteries 6485 4.2. Capacitors 6485 5. Chemical Energy Storage: Solar Fuels 6486 5.1. Solar Fuels in Nature 6486 5.2. Artificial Photosynthesis and General Considerations of Water Splitting 6486

Solar Energy Supply and Storage for the Legacy and Nonlegacy Worlds

A detailed investigation has been carried out of the structure and electrochemical activity of electrodeposited Ni-Fe films for the oxygen evolution reaction (OER) in alkaline electrolytes. Ni-Fe films with a bulk and surface composition of 40% Fe exhibit OER activities that are roughly 2 orders of magnitude higher than that of a freshly deposited Ni film and about 3 orders of magnitude higher than that of an Fe film. The freshly deposited Ni film increases in activity by as much as 20-fold during exposure to the electrolyte (KOH); however, all films containing Fe are stable as deposited. The oxidation of Ni(OH)2 to NiOOH in Ni films occurs at potentials below the onset of the OER. Incorporation of Fe into the film increases the potential at which Ni(OH)2/NiOOH redox occurs and decreases the average oxidation state of Ni in NiOOH. The Tafel slope (40 mV dec(-1)) and reaction order in OH(-) (1) for the mixed Ni-Fe films (containing up to 95% Fe) are the same as those for aged Ni films. In situ Raman spectra acquired in 0.1 M KOH at OER potentials show two bands characteristic of NiOOH. The relative intensities of these bands vary with Fe content, indicating a change in the local environment of Ni-O. Similar changes in the relative intensities of the bands and an increase in OER activity are observed when pure Ni films are aged. These observations suggest that the OER is catalyzed by Ni in Ni-Fe films and that the presence of Fe alters the redox properties of Ni, causing a positive shift in the potential at which Ni(OH)2/NiOOH redox occurs, a decrease in the average oxidation state of the Ni sites, and a concurrent increase in the activity of Ni cations for the OER.

/pdf/an-investigation-of-thin-film-ni-fe-oxide-catalysts-for-the-320q9jyo15.pdf

An Investigation of Thin-Film Ni–Fe Oxide Catalysts for the Electrochemical Evolution of Oxygen

Electrode reaction rates and most double layer parameters are extensive quantities and have to be referred to the unit area of the interface. Knowledge of the real surface area of electrodes is therefore needed. Different methods have been proposed to normalize experimental data specifically with solid electrodes. Some of them are not sufficiently justified from a physical point of view. A few of them are definitely questionable. The purpose of this document is to scrutinize the basis on which the various methods and approaches rest, in order to assess their relevance to the specific electrochemical situation and, as far as possible, their absolute reliability

Real surface area measurements in electrochemistry

Adsorption of Organic Compounds on Electrodes

Three periods of Pt–Ru research are considered step-by-step: the initial period after discovery (1963–1970); observation and classification of basic tendencies (like the effects of composition, segregation, structural features on the activity; up to 1990); nanostructural studies and molecular level consideration of electrocatalytic phenomena in combination with advanced applied studies of materials, mechanistic, and applied aspects (after 1990). The main idea of this review is to balance various aspects of Pt–Ru electrochemistry related to material science and electrocatalysis as well as to remember the early basic results being of importance for future understanding of Pt–Ru functional properties.

Oleg A. Petrii

Papers

Real surface area measurements in electrochemistry

Real surface area measurements in electrochemistry

Adsorption of Organic Compounds on Electrodes

Pt–Ru electrocatalysts for fuel cells: a representative review

Potentials of zero total and zero free charge of platinum group metals