Fe plays a critical, but not yet understood, role in enhancing the activity of the Ni-based oxygen evolution reaction (OER) electrocatalysts. We report electrochemical, in situ electrical, photoelectron spectroscopy, and X-ray diffraction measurements on Ni1–xFex(OH)2/Ni1–xFexOOH thin films to investigate the changes in electronic properties, OER activity, and structure as a result of Fe inclusion. We developed a simple method for purification of KOH electrolyte that uses precipitated bulk Ni(OH)2 to absorb Fe impurities. Cyclic voltammetry on rigorously Fe-free Ni(OH)2/NiOOH reveals new Ni redox features and no significant OER current until >400 mV overpotential, different from previous reports which were likely affected by Fe impurities. We show through controlled crystallization that β-NiOOH is less active for OER than the disordered γ-NiOOH starting material and that previous reports of increased activity for β-NiOOH are due to incorporation of Fe-impurities during the crystallization process. Through...

Nickel–Iron Oxyhydroxide Oxygen-Evolution Electrocatalysts: The Role of Intentional and Incidental Iron Incorporation

Sunlight is by far the most plentiful renewable energy resource, providing Earth with enough power to meet all of humanity's needs several hundred times over. However, it is both diffuse and intermittent, which presents problems regarding how best to harvest this energy and store it for times when the sun is not shining. Devices that use sunlight to split water into hydrogen and oxygen could be one solution to these problems, because hydrogen is an excellent fuel. However, if such devices are to become widely adopted, they must be cheap to produce and operate. Therefore, the development of electrocatalysts for water splitting that comprise only inexpensive, earth-abundant elements is critical. In this Review, we investigate progress towards such electrocatalysts, with special emphasis on how they might be incorporated into photoelectrocatalytic water-splitting systems and the challenges that remain in developing these devices. Splitting water is an attractive means by which energy — either electrical and/or light — is stored and consumed on demand. Active and efficient catalysts for anodic and cathodic reactions often require precious metals. This Review covers base-metal catalysts that can afford high performance in a more sustainable and available manner.

Earth-abundant catalysts for electrochemical and photoelectrochemical water splitting

Bismuth vanadate (BiVO4) has a band structure that is well-suited for potential use as a photoanode in solar water splitting, but it suffers from poor electron-hole separation. Here, we demonstrate that a nanoporous morphology (specific surface area of 31.8 square meters per gram) effectively suppresses bulk carrier recombination without additional doping, manifesting an electron-hole separation yield of 0.90 at 1.23 volts (V) versus the reversible hydrogen electrode (RHE). We enhanced the propensity for surface-reaching holes to instigate water-splitting chemistry by serially applying two different oxygen evolution catalyst (OEC) layers, FeOOH and NiOOH, which reduces interface recombination at the BiVO4/OEC junction while creating a more favorable Helmholtz layer potential drop at the OEC/electrolyte junction. The resulting BiVO4/FeOOH/NiOOH photoanode achieves a photocurrent density of 2.73 milliamps per square centimenter at a potential as low as 0.6 V versus RHE.

https://science.sciencemag.org/content/sci/early/2014/02/12/science.1246913.full.pdf

Nanoporous BiVO4 Photoanodes with Dual-Layer Oxygen Evolution Catalysts for Solar Water Splitting

Although sunlight-driven water splitting is a promising route to sustainable hydrogen fuel production, widespread implementation is hampered by the expense of the necessary photovoltaic and photoelectrochemical apparatus. Here, we describe a highly efficient and low-cost water-splitting cell combining a state-of-the-art solution-processed perovskite tandem solar cell and a bifunctional Earth-abundant catalyst. The catalyst electrode, a NiFe layered double hydroxide, exhibits high activity toward both the oxygen and hydrogen evolution reactions in alkaline electrolyte. The combination of the two yields a water-splitting photocurrent density of around 10 milliamperes per square centimeter, corresponding to a solar-to-hydrogen efficiency of 12.3%. Currently, the perovskite instability limits the cell lifetime.

http://science.sciencemag.org/content/sci/345/6204/1593.full.pdf

Water photolysis at 12.3% efficiency via perovskite photovoltaics and Earth-abundant catalysts

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

Large-scale electrolysis of water for hydrogen generation requires better catalysts to lower the kinetic barriers associated with the oxygen evolution reaction (OER). Although most OER catalysts are based on crystalline mixed-metal oxides, high activities can also be achieved with amorphous phases. Methods for producing amorphous materials, however, are not typically amenable to mixed-metal compositions. We demonstrate that a low-temperature process, photochemical metal-organic deposition, can produce amorphous (mixed) metal oxide films for OER catalysis. The films contain a homogeneous distribution of metals with compositions that can be accurately controlled. The catalytic properties of amorphous iron oxide prepared with this technique are superior to those of hematite, whereas the catalytic properties of a-Fe100-y-zCoyNizOx are comparable to those of noble metal oxide catalysts currently used in commercial electrolyzers.

https://science.sciencemag.org/content/sci/early/2013/03/27/science.1233638.full.pdf

Photochemical Route for Accessing Amorphous Metal Oxide Materials for Water Oxidation Catalysis

The effects of replacing a single polypyridyl ligand with an analogous anionic cyclometalating ligand were investigated for a set of three structurally related series of Ru(II) compounds formulated as [Ru(bpy)2(L)]z, [Ru(tpy)(L)]z, and [Ru(tpy)(L)Cl]z, where z = 0, +1, or +2, and L = polypyridyl (e.g., bpy = 2,2′-bipyridine, tpy = 2,2′:6′,2′′-terpyridine) or cyclometalating ligand (e.g., deprotonated forms of 2-phenylpyridine or 3−(2−pyridinyl)-benzoic acid). Each of the complexes were synthesized and characterized by 1H NMR spectroscopy, electrospray ionization mass spectrometry (ESI-MS), and/or elemental analyses (EA). Cyclic voltammetry reveals that cyclometalation causes a shift of the first oxidation and reduction potentials by −0.5 to −0.8 V and −0.2 to −0.4 V, respectively, relative to their polypyridyl congeners. These disparate shifts have the effect of inducing a bathochromic shift of the lowest-energy absorption bands by as much as 90 nm. With the aid of time-dependent density functional theory...

On the Viability of Cyclometalated Ru(II) Complexes for Light-Harvesting Applications

Photochemical metal-organic deposition produces amorphous (mixed) metal oxide films, which show high electrocatalytic activity for the oxygen evolution reaction.

Photochemical Route for Accessing Amorphous Metal Oxide Materials for Water Oxidation Catalysis.

Sol–gel reaction conditions that enable the growth of one-dimensional (1D) anatase titanium dioxide (TiO2) nanostructures from fluorine-doped indium tin oxide (FTO) substrates are described. The generation of these linear nanostructures is achieved using acetic acid (HOAc) and titanium isopropoxide (Ti(OiPr)4) in anhydrous heptane in the absence of an external bias or template. The procedure requires the functionalization of base-treated substrates with Ti-oxide nucleation sites, which serve as a foundation for the growth of linear Ti-oxide macromolecules. Calcination of these macromolecules at 450 °C under an ambient atmosphere produce uniform films of randomly oriented anatase TiO2 nanowires. The nucleation and growth processes are both acutely sensitive to the relative molar ratio (R) of HOAc to Ti(OiPr)4. Optimal surface coverage of the nucleation sites is observed when the R value utilized for the nucleation phase (denoted Ri) is equal to 1.3. The highest quality nanowire films were obtained when the R value employed during the gelation phase (denoted Rf) was held between 8.5 and 14. Characterization of the films by electron microscopy revealed a uniform film of disordered anatase TiO2 nanowires with high aspect ratios. The dimensions of the nanostructures correspond to lengths of ca. 1–10 μm and widths of 54 ± 10 nm. High-resolution transmission electron microscopy (HRTEM) and X-ray diffraction (XRD) techniques demonstrate that the anatase nanowires are a linear arrangement of crystallites ranging in size from 13 to 19 nm. A systematic evaluation of how reaction conditions (e.g., solvent volume, stoichiometry of reagents, substrate base treatment) affect the generation of these TiO2 films is presented.

Pavel A. Sedach

Papers

Photochemical Route for Accessing Amorphous Metal Oxide Materials for Water Oxidation Catalysis

On the Viability of Cyclometalated Ru(II) Complexes for Light-Harvesting Applications

Photochemical Route for Accessing Amorphous Metal Oxide Materials for Water Oxidation Catalysis.

Solution growth of anatase TiO2 nanowires from transparent conducting glass substrates