The electrosynthesis of ammonia from nitrogen and water is a topic of considerable interest in the quest for sustainable and decentralized NH3 production. Tin(II) phthalocyanine complexes have been proposed as electrocatalysts for nitrogen reduction to ammonia in aqueous solution, with Faradaic yields approaching 2% having been reported. Herein, however, we show that such complexes are not electrocatalysts for this transformation, with the amount of ammonia detected being essentially the same under N2 and under Ar. Instead, we suggest that apparent ammonia generation could arise either through contaminants in the as-prepared tin(II) phthalocyanine complexes, or by the electro-decomposition of these complexes under cathodic bias.

Metal chalcogenides, and doped molybdenum sulfides in particular, have considerable potential as earth-abundant electrocatalysts for the hydrogen evolution reaction. This is especially true in the case of solar-to-hydrogen devices, where an ability to deposit these materials on transparent substrates is therefore desirable. Hydrothermal methods are perhaps the most common route by which metal chalcogenide materials suitable for the hydrogen evolution reaction are produced. Such methods are simple and scalable, but the direct hydrothermal deposition of metal chalcogenides on transparent oxide electrodes has hitherto never been reported. Such an advance would greatly facilitate the expansion of the field by removing the requirement for separate hydrothermal-synthesis and catalyst-deposition steps. In this paper, we show that the ternary chalcogenide Co2Mo9S26 can be synthesised on a fluorine-doped tin oxide substrate by hydrothermal methods directly from solutions of the simple metal salts. These films display good activity for the hydrogen evolution reaction from acid solution, achieving current densities of 10 mA cm−2 at 260 mV overpotential with a Tafel slope of 64 mV per decade. Moreover, the resulting films can be made to be translucent, a very useful property which would allow light to be transmitted through the catalyst to an underlying light-harvesting array in any solar-to-hydrogen device employing this material at the cathode.

The electrocatalytic hydrogen evolution reaction (HER) is of considerable interest for the production of H2 from sustainable sources. Herein, we show that under conditions commonly employed in identifying new electrocatalysts for this reaction (using Ag/AgCl reference electrodes in 1 M H2SO4), silver ions can leak from the reference electrode into solution and then deposit on the working electrode as Ag(0), giving current densities for the HER of over 5 mA cm–2 at ∼500 mV overpotential. This is well within the activity range reported for many electrocatalysts of the HER and calls into question the validity of any reports using Ag/AgCl reference electrodes which either fail to explicitly exclude silver as a cause of the electrocatalytic activity or else cannot demonstrate significantly superior activity to this baseline.Keywords: contamination; electrocatalysis; hydrogen evolution; impurity; silver; solar fuels; water splitting;

Solar-to-hydrogen photoelectrochemical cells (PECs) have been proposed as a means of converting sunlight into H2 fuel. However, in traditional PECs, the oxygen evolution reaction and the hydrogen evolution reaction are coupled, and so the rate of both of these is limited by the photocurrents that can be generated from the solar flux. This in turn leads to slow rates of gas evolution that favor crossover of H2 into the O2 stream and vice versa, even through ostensibly impermeable membranes such as Nafion. Herein, we show that the use of the electron-coupled-proton buffer (ECPB) H3PMo12O40 allows solar-driven O2 evolution from water to proceed at rates of over 1 mA cm–2 on WO3 photoanodes without the need for any additional electrochemical bias. No H2 is produced in the PEC, and instead H3PMo12O40 is reduced to H5PMo12O40. If the reduced ECPB is subjected to a separate electrochemical reoxidation, then H2 is produced with full overall Faradaic efficiency.

As our reliance on renewable energy resources increases, so will our need to store this energy in the form of chemical fuels to iron-out peaks and troughs in supply. Sunlight, the most plentiful source of renewable energy, is especially problematic in this regard as it is so diffuse. One way to convert solar irradiation to fuels effectively would be to develop large surface area photo-electrochemical devices that could use sunlight directly to split water into H2 and O2. However, in order to be feasible, such an approach requires that these devices (and their components) are extremely cheap. In this review, we will discuss catalysts for the water oxidation half-reaction of electrochemical water splitting that can be produced by electrodeposition (a technique well suited to large-scale, low-cost applications), and that are based on the comparatively plentiful and inexpensive first row transition metals. Special attention will be paid to the electrodeposition conditions used in the various examples given, and structure–function relationships for electrochemical water oxidation for the materials produced by these techniques will be elucidated.

The oxides of nitrogen (chiefly NO, NO3−, NO2− and N2O) are key components of the natural nitrogen cycle and are intermediates in a range of processes of enormous biological, environmental and industrial importance. Nature has evolved numerous enzymes which handle the conversion of these oxides to/from other small nitrogen-containing species and there also exist a number of heterogeneous catalysts that can mediate similar reactions. In the chemical space between these two extremes exist metal–ligand coordination complexes that are easier to interrogate than heterogeneous systems and simpler in structure than enzymes. In this Tutorial Review, we will examine catalysts for the inter-conversions of the various nitrogen oxides that are based on such complexes, looking in particular at more recent examples that take inspiration from the natural systems.

Electrolytic water oxidation using earth-abundant elements is a key challenge in the quest to develop cheap, large surface area arrays for solar-to-hydrogen conversion. There have been numerous studies in this area in recent years, but there remains an imperative to demonstrate that the current densities reported are indeed due to the species under consideration and not due to the presence of adventitious (yet possibly highly active) contaminants at low levels. Herein, we show that adventitious nickel at concentrations as low as 17 nM can act as a water oxidation catalyst in mildly basic aqueous solutions, achieving stable (tens of hours) current densities of 1 mA cm–2 at overpotentials as low as 540 mV at pH 9.2 and 400 mV at pH 13. This nickel was not added to the electrolysis baths deliberately, but it was found to be present in the electrolytes as an impurity by ICP-MS. The presence of nickel on anodes from extended-time bulk electrolysis experiments was confirmed by XPS. In showing that such low levels of nickel can perform water oxidation at overpotentials comparable to many recently reported water oxidation catalysts, this work serves to raise the burden of proof required of new materials in this field: contamination by adventitious metal ions at trace loadings must be excluded as a possible cause of any observed water oxidation activity.

Typical catalysts for the electrolysis of water at low pH are based on precious metals (Pt for the cathode and IrO2 or RuO2 for the anode). However, these metals are rare and expensive, and hence lower cost and more abundant catalysts are needed if electrolytically produced hydrogen is to become more widely available. Herein, we show that electrode-film formation from aqueous solutions of first row transition metal ions at pH 1.6 can be induced under the action of an appropriate cell bias and that in the case of cobalt voltages across the cell in excess of 2 V lead to the formation of a pair of catalysts that show functional stability for oxygen evolution and proton reduction for over 24 h. We show that these films are metastable and that if the circuit is opened, they redissolve into the electrolyte bath with concomitant O2 and H2 evolution, such that the overall Faradaic efficiency for charge into the system versus amounts of gases obtained approaches unity for both O2 and H2. This work highlights the ability of first row transition metals to mediate heterogeneous electrolytic water splitting in acidic media by exploiting, rather than trying to avoid, the natural propensity of the catalysts to dissolve at the low pHs used. This in turn we hope will encourage others to examine the promise of metastable electrocatalysts based on abundant elements for a range of reactions for which they have traditionally been overlooked on account of their perceived instability under the prevailing conditions.

As our reliance on renewable energy resources increases, so will our need to store this energy in the form of chemical fuels to iron-out peaks and troughs in supply. Sunlight, the most plentiful source of renewable energy, is especially problematic in this regard as it is so diffuse. One way to convert solar irradiation to fuels effectively would be to develop large surface area photo-electrochemical devices that could use sunlight directly to split water into H2 and O2. However, in order to be feasible, such an approach requires that these devices (and their components) are extremely cheap. In this review, we will discuss catalysts for the water oxidation half-reaction of electrochemical water splitting that can be produced by electrodeposition (a technique well suited to large-scale, low-cost applications), and that are based on the comparatively plentiful and inexpensive first row transition metals. Special attention will be paid to the electrodeposition conditions used in the various examples given, and structure–function relationships for electrochemical water oxidation for the materials produced by these techniques will be elucidated.

The oxides of nitrogen (chiefly NO, NO3−, NO2− and N2O) are key components of the natural nitrogen cycle and are intermediates in a range of processes of enormous biological, environmental and industrial importance. Nature has evolved numerous enzymes which handle the conversion of these oxides to/from other small nitrogen-containing species and there also exist a number of heterogeneous catalysts that can mediate similar reactions. In the chemical space between these two extremes exist metal–ligand coordination complexes that are easier to interrogate than heterogeneous systems and simpler in structure than enzymes. In this Tutorial Review, we will examine catalysts for the inter-conversions of the various nitrogen oxides that are based on such complexes, looking in particular at more recent examples that take inspiration from the natural systems.

Metal chalcogenides, and doped molybdenum sulfides in particular, have considerable potential as earth-abundant electrocatalysts for the hydrogen evolution reaction. This is especially true in the case of solar-to-hydrogen devices, where an ability to deposit these materials on transparent substrates is therefore desirable. Hydrothermal methods are perhaps the most common route by which metal chalcogenide materials suitable for the hydrogen evolution reaction are produced. Such methods are simple and scalable, but the direct hydrothermal deposition of metal chalcogenides on transparent oxide electrodes has hitherto never been reported. Such an advance would greatly facilitate the expansion of the field by removing the requirement for separate hydrothermal-synthesis and catalyst-deposition steps. In this paper, we show that the ternary chalcogenide Co2Mo9S26 can be synthesised on a fluorine-doped tin oxide substrate by hydrothermal methods directly from solutions of the simple metal salts. These films display good activity for the hydrogen evolution reaction from acid solution, achieving current densities of 10 mA cm−2 at 260 mV overpotential with a Tafel slope of 64 mV per decade. Moreover, the resulting films can be made to be translucent, a very useful property which would allow light to be transmitted through the catalyst to an underlying light-harvesting array in any solar-to-hydrogen device employing this material at the cathode.

Complexes of Co(III) containing mixed chelating diimine and o-quinone ligand sets are of fundamental interest on account of their fascinating magnetic and electronic properties. Whilst complexes of this type containing one diimine and two o-quinone ligands have been studied extensively, those with the reverse stoichiometry (two diimines and one o-quinone) are much rarer. Herein, we describe a ready route to the synthesis of the complex [CoIII(o-catecholate) (2,2′-bipyridine)2]+ (1), and also report the synthesis of [CoIII(o-catecholate)(5,5′-dimethyl-2,2′-bipyridine)2]+ (2) and [CoIII(o-benezenedithiolate)(5,5′-dimethyl-2,2′-bipyridine)2]+ (3) for the first time. Spectroscopic studies show that complex 2 displays intriguing solvatochromic behaviour as a function of solvent hydrogen bond donation ability, a property of this type of complex which has hitherto not been reported. Time-dependent density function theory (TD-DFT) shows that this effect arises as a result of hydrogen bonding between the solvent and the oxygen atoms of the catecholate ligand. In contrast, the sulfur atoms in the benzenedithiolate analogue 3 are much weaker acceptors of hydrogen bonds from the solvent, meaning that complex 3 is only very weakly solvatochromic. Finally, we show that complex 2 has some potential as a molecular probe that can report on the composition of mixed solvent systems as a function of its absorbance spectrum.