First row transition metal catalysts for solar-driven water oxidation produced by electrodeposition

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

Efficient electrocatalytic water oxidation at neutral and high pH by adventitious nickel at nanomolar concentrations

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

Probing the effects of steric bulk on the solution-phase behaviour and redox chemistry of cobalt-diimine complexes

Cobalt-diimine complexes are important structural and redox-active elements in supramolecular assemblies. However, functionalisation of the diimine ligand adjacent to the N-donor atoms can affect dramatically the types of Co-diimine complexes that can form and their redox activity. Herein, we compare the solution phase and redox chemistry of Co(II) complexes with 1,10-phenanthroline, 5,5′-dimethyl-2,2′-bipyridine and 2,9-dimethyl-1,10-phenanthroline (neocuproine). In acetonitrile solutions containing Co(NO3)2 and neocuproine, the dominant species is the mono-diimine complex [Co(neocuproine)(NO3)(CH3CN)2]+. This complex cannot be oxidised, either electrochemically nor with iodine. We rationalise this behaviour by considering the steric constraints placed upon the metal centre by the bulky methyl substituents on the neocuproine ligand. Furthermore, from solutions of [Co(neocuproine)(NO3)(CH3CN)2]+, crystals of formula [Co(neocuproine)2(NO3)]+·[Co(neocuproine)(NO3)3]− can be obtained. We believe that this work will guide the development of Co-diimine supramolecular assemblies by highlighting the extent to which substituents close to the N-donor atoms affect which species form in solution, and their likely redox activity

Recent progress towards the electrosynthesis of ammonia from sustainable resources

Ammonia (NH3) is a key commodity chemical of vital importance for fertilisers. It is made on an industrial scale via the Haber Bosch process, which requires significant infrastructure to be in place such that ammonia is generally made in large, centralized facilities. If ammonia could be produced under less demanding conditions, then there would be the potential for smaller devices to be used to generate ammonia in a decentralized manner for local consumption. Electrochemistry has been proposed as an enabling technology for this purpose as it is relatively simple to scale electrolytic devices to meet almost any level of demand. Moreover, it is possible to envisage electrosynthetic cells where water could be oxidised to produce protons and electrons at the anode which could then be used to reduce and protonate nitrogen to give ammonia at the cathode. If this nitrogen were sourced from the air, then the only required infrastructure for this process would be supplies of water, air and electricity, the latter of which could be provided by renewables. Hence an electrosynthetic cell for ammonia production could allow NH3 to be generated sustainably in small, low-cost devices requiring only minimal facilities. In this review, we describe recent progress towards such electrosynthetic ammonia production devices, summarizing also some of the seminal literature in the field. Comparison is made between the various different approaches that have been taken, and the key remaining challenges in the electrosynthesis of ammonia are highlighted

Combining 3D printing and liquid handling to produce user-friendly reactionware for chemical synthesis and purification

We use two 3D-printing platforms as solid- and liquid-handling fabricators, producing sealed reactionware for chemical synthesis with the reagents, catalysts and purification apparatus integrated into monolithic devices. Using this reactionware, a multi-step reaction sequence was performed by simply rotating the device so that the reaction mixture flowed through successive environments under gravity, without the need for any pumps or liquid-handling prior to product retrieval from the reactionware in a pure form

A re-evaluation of Sn(II) phthalocyanine as a catalyst for the electrosynthesis of ammonia

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

An investigation into the unusual linkage isomerization and nitrite reduction activity of a novel tris(2-pyridyl) copper complex

The copper-containing nitrite reductases (CuNIRs) are a class of enzymes that mediate the reduction of nitrite to nitric oxide in biological systems. Metal–ligand complexes that reproduce the salient features of the active site of CuNIRs are therefore of fundamental interest, both for elucidating the possible mode of action of the enzymes and for developing biomimetic catalysts for nitrite reduction. Herein, we describe the synthesis and characterization of a new tris(2-pyridyl) copper complex ([Cu1(NO2)2]) that binds two molecules of nitrite, and displays all three of the common binding modes for NO2−, with one nitrite bound in an asymmetric quasi-bidentate κ2-ONO manner and the other bound in a monodentate fashion with a linkage isomerism between the κ1-ONO and κ1-NO2 binding modes. We use density functional theory to help rationalize the presence of all three of these linkage isomers in one compound, before assessing the redox activity of [Cu1(NO2)2]. These latter studies show that the complex is not a competent nitrite reduction electrocatalyst in non-aqueous solvent, even in the presence of additional proton donors, a finding which may have implications for the design of biomimetic catalysts for nitrite reduction

Walking Molecules

Inspired by the motor protein kinesin, an ambitious and unprecedented mimic is proposed – a synthetic molecular motor that can walk. This thesis aims to explain the basic principles which define such walking molecules, with reference to both natural and synthetic systems. In light of these tenets, the rational design of the proposed synthetic kinesin analogue will then be expounded. The putative design envisages the use of a series of stimuli-induced binding events to cause a “walker unit” to process along a polypyridyl track in a unidirectional, hand-over-hand fashion. The chemistry behind the stepping mechanisms of both feet of the walker unit will be discussed in detail, along with a complete description of the synthesis of the track and walker unit to date. The future challenges and potential applications of the proposed system will be addressed

Decoupled electrolysis using a silicotungstic acid electron-coupled-proton buffer in a proton exchange membrane cell

The storage of renewably-generated energy as hydrogen via the electrolysis of water is a fundamental cornerstone of a sustainable hydrogen economy. Conventional electrolysers usually require stable power inputs in order to operate effectively and safely and so may be unsuited to harnessing renewable power, which is often intermittent and diffuse. Electrolysis mediated by Electron-Coupled-Proton Buffers has the potential to overcome some of the challenges surrounding electrolysis using low and/or sporadic power inputs (especially those related to gas crossover) as the use of Electron-Coupled-Proton Buffers allows the oxygen and hydrogen evolution reactions to be completely decoupled from one another. Herein, we show that silicotungstic acid can be used as an Electron-Coupled-Proton Buffer in a proton exchange membrane cell, decoupling the hydrogen and oxygen evolution reactions at steady state current densities as high as 500 mA cm−2. O2 and H2 can be produced continuously by this system by cycling a fixed volume of the Electron-Coupled-Proton Buffer solution. Even at current densities as low as 25 mA cm−2, the level of hydrogen in the oxygen stream is <0.4%, whereas a conventional proton exchange membrane electrolyser operating at this current density produces oxygen containing nearly 2% hydrogen (unacceptable for most applications). Furthermore, using silicotungstic acid as an Electron-Coupled-Proton Buffer also confers greater tolerance to non-deionised water inputs and reduces fluoride release from the perfluorosulfonated membrane (a marker for membrane degradation) relative to a conventional proton exchange membrane electrolyser. Together, these results highlight the promise and potential advantages of Electron-Coupled-Proton Buffers (and silicotungstic acid in particular) for the electrolytic production of hydrogen and oxygen over a wide range of current densities, such as might be produced by renewable power inputs

Characterising the cavitation activity generated by an ultrasonic horn at varying tip-vibration amplitudes

Dual-perspective high-speed imaging and acoustic detection is used to characterise cavitation activity at the tip of a commercial 20 kHz (f0) ultrasonic horn, over 2 s sonications across the range of input powers available (20 – 100%). Imaging at 1 × 105 frames per second (fps) captures cavitation-bubble cluster oscillation at the horn-tip for the duration of the sonication. Shadowgraphic imaging at 2 Mfps, from an orthogonal perspective, probes cluster collapse and shock wave generation at higher temporal resolution, facilitating direct correlation of features within the acoustic emission data generated by the bubble activity. f0/m subharmonic collapses of the primary cavitation cluster directly beneath the tip, with m increasing through integer values at increasing input powers, are studied. Shock waves generated by periodic primary cluster collapses dominate the non-linear emissions of the cavitation noise spectra. Transitional input powers for which the value of m is indistinct, are identified. Overall shock wave content within the emission signals collected during sonications at transitional input powers are reduced, relative to input powers with distinct m. The findings are relevant for the optimisation of applications such as sonochemistry, known to be mediated by bubble collapse phenomena