Oxygen-tolerant proton reduction catalysis: Much O<inf>2</inf> about nothing?

This perspective summarises strategies for avoiding adverse effects of O2 on H2-evolving enzymatic systems, molecular synthetic catalysts and catalytic surfaces.Financial support from the EPSRC (EP/H00338X/2), the Christian Doppler Research Association (Austrian Federal Ministry of Science, Research and Economy and National Foundation for Research, Technology and Development), and the OMV Group is gratefully acknowledged.This is the final version of the article. It first appeared from the Royal Society of Chemistry via http://dx.doi.org/10.1039/C5EE01167

Solar-driven reforming of lignocellulose to H2_{2} with a CdS/CdOx_{x} photocatalyst

Lignocellulose is Earth’s most abundant form of biomass and its valorization to H$_{2}$ is a key objective for the generation of renewable fuels. Solar-driven photocatalytic reforming of lignocellulose to H$_{2}$ at ambient temperature offers a sustainable route towards this goal, but this reaction is currently limited to noble-metal-containing systems that operate with low activity under ultraviolet light. Here, we report the light-driven photoreforming of cellulose, hemicellulose and lignin to H$_{2}$ using semiconducting cadmium sulfide quantum dots in alkaline aqueous solution. We show that basic conditions cause these dots to become coated with oxide/hydroxide in situ, presenting a strategy to improve their photocatalytic performance. The system operates under visible light, is stable beyond six days and is even able to reform unprocessed lignocellulose, such as wood and paper, under solar irradiation at room temperature, presenting an inexpensive route to drive aqueous proton reduction to H$_{2}$ through waste biomass oxidation.This work was supported by the Christian Doppler Research Association (Austrian Federal Ministry of Science, Research and Economy and the National Foundation for Research, Technology and Development), the OMV Group (to E.R.), the EPSRC (DTA studentships for D.W.W. and T.E.R), the Isaac Newton Trust, the German Research Foundation (to M.F.K.), the World Premier Institute Research Center Initiative (WPI), MEXT, Japan (to K.L.O.) and a Marie Curie Research fellowship (to K.H.L., GAN 701192 - VSHER)

Competing charge transfer pathways at the photosystem II-electrode interface.

The integration of the water-oxidation enzyme photosystem II (PSII) into electrodes allows the electrons extracted from water oxidation to be harnessed for enzyme characterization and to drive novel endergonic reactions. However, PSII continues to underperform in integrated photoelectrochemical systems despite extensive optimization efforts. Here we carried out protein-film photoelectrochemistry using spinach and Thermosynechococcus elongatus PSII, and we identified a competing charge transfer pathway at the enzyme-electrode interface that short-circuits the known water-oxidation pathway. This undesirable pathway occurs as a result of photo-induced O2 reduction occurring at the chlorophyll pigments and is promoted by the embedment of PSII in an electron-conducting fullerene matrix, a common strategy for enzyme immobilization. Anaerobicity helps to recover the PSII photoresponse and unmasks the onset potentials relating to the QA/QB charge transfer process. These findings impart a fuller understanding of the charge transfer pathways within PSII and at photosystem-electrode interfaces, which will lead to more rational design of pigment-containing photoelectrodes in general.This work was supported by the U.K. Engineering and Physical Sciences Research Council (EP/H00338X/2 to E. Reisner), the U.K. Biology and Biotechnological Sciences Research Council (BB/K010220/1 to E. Reisner), a Marie Curie International Incoming Fellowship (PIIF-GA-2012-328085 RPSII to J.J.Z.). N.P. was supported by the Winton Fund for the Physics of Sustainability. E. Romero. and R.v.G. were supported by the VU University Amsterdam, the Laserlab-Europe Consortium, the TOP grant (700.58.305) from the Foundation of Chemical Sciences part of NWO, the Advanced Investigator grant (267333, PHOTPROT) from the European Research Council, and the EU FP7 project PAPETS (GA 323901). R.v.G. gratefully acknowledges his `Academy Professor' grant from the Royal Netherlands Academy of Arts and Sciences (KNAW). We would also like to thank Miss Katharina Brinkert and Prof A. William Rutherford for a sample of T. elongatus PSII, and H. v. Roon for preparation of the spinach PSII samples

Plastic waste as a feedstock for solar-driven H<inf>2</inf> generation

Plastic waste is recycled to hydrogen using sunlight and a CdS photocatalyst.Christian Doppler Research Association (Austrian Federal Ministry of Science, Research and Economy and the National Foundation for Research, Technology and Development), OMV group, EPSRC (NanoDTC studentship, STA studentship, IAA Follow-on fund)

Microbial biogeography of 925 geothermal springs in New Zealand

© 2018, The Author(s). Geothermal springs are model ecosystems to investigate microbial biogeography as they represent discrete, relatively homogenous habitats, are distributed across multiple geographical scales, span broad geochemical gradients, and have reduced metazoan interactions. Here, we report the largest known consolidated study of geothermal ecosystems to determine factors that influence biogeographical patterns. We measured bacterial and archaeal community composition, 46 physicochemical parameters, and metadata from 925 geothermal springs across New Zealand (13.9–100.6 °C and pH 70 °C. Further, community dissimilarity increases with geographic distance, with niche selection driving assembly at a localised scale. Surprisingly, two genera (Venenivibrio and Acidithiobacillus) dominated in both average relative abundance (11.2% and 11.1%, respectively) and prevalence (74.2% and 62.9%, respectively). These findings provide an unprecedented insight into ecological behaviour in geothermal springs, and a foundation to improve the characterisation of microbial biogeographical processes