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

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

The role of ecolabeling in fisheries management and conservation

Author Posting. © The Authors, 2005. This is the author's version of the work. It is posted here by permission of Blackwell for personal use, not for redistribution. The definitive version was published in Conservation Biology 20 (2006): 392-398, doi:10.1111/j.1523-1739.2006.00319.x.The Marine Stewardship Council (MSC) regulate the ecolabeling of products from fisheries with the aim of promoting sustainable fishery practices. To date 11 fisheries have attained full certification and a further 7 are under review. Together these fisheries offer 220 ecolabeled marine products to consumers. Despite great potential to encourage sustainable fisheries, and thereby bring conservation benefits to marine systems, there are a range of issues that may serve to limit the wider uptake of MSC ecolabeled products. These include a general lack of consumer concern for marine fish and sustainable fisheries, an absence of guaranteed continued financial benefits to participating fishers and difficulties of quality assurance which are related to the complexities in monitoring compliance of marine fisheries. In addition, it is apparent that property-rights over the fishery seem to be an essential prerequisite for engagement in MSC and this is one major impediment to wider uptake of the scheme in current marine fisheries, which tend to be open access. Some modifications to the current scheme may be needed if wider participation of marine fishers is to be achieved. These may include a tiered approach to certification, certification of fishers rather than fisheries, governmental facilitation to assist the latter, and greater engagement with retailers and buyers rather than individual consumers. None of these changes will occur without constructive engagement of Government, retailers and the fishing industry.MJK was part funded through a Marine Policy Center Senior Research Fellowship