Scalable Photocatalyst Panels for Photoreforming of Plastic, Biomass and Mixed Waste in Flow.

Solar-driven reforming uses sunlight and a photocatalyst to generate H2 fuel from waste at ambient temperature and pressure. However, it faces practical scaling challenges such as photocatalyst dispersion and recyclability, competing light absorption by the waste solution, slow reaction rates and low conversion yields. Here, the immobilisation of a noble-metal-free carbon nitride/nickel phosphide (CNx |Ni2 P) photocatalyst on textured glass is shown to overcome several of these limitations. The 1 cm2 CNx |Ni2 P panels photoreform plastic, biomass, food and mixed waste into H2 and organic molecules with rates comparable to those of photocatalyst slurries. Furthermore, the panels enable facile photocatalyst recycling and novel photoreactor configurations that prevent parasitic light absorption, thereby promoting H2 production from turbid waste solutions. Scalability is further verified by preparing 25 cm2 CNx |Ni2 P panels for use in a custom-designed flow reactor to generate up to 21 μmolH 2  m-2  h-1 under "real-world" (seawater, low sunlight) conditions. The application of inexpensive and readily scalable CNx |Ni2 P panels to photoreforming of a variety of real waste streams provides a crucial step towards the practical deployment of this technology

A Precious-Metal-Free Hybrid Electrolyzer for Alcohol Oxidation Coupled to CO2 -to-Syngas Conversion.

Electrolyzers combining CO2 reduction (CO2 R) with organic substrate oxidation can produce fuel and chemical feedstocks with a relatively low energy requirement when compared to systems that source electrons from water oxidation. Here, we report an anodic hybrid assembly based on a (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) electrocatalyst modified with a silatrane-anchor (STEMPO), which is covalently immobilized on a mesoporous indium tin oxide (mesoITO) scaffold for efficient alcohol oxidation (AlcOx). This molecular anode was subsequently combined with a cathode consisting of a polymeric cobalt phthalocyanine on carbon nanotubes to construct a hybrid, precious-metal-free coupled AlcOx-CO2 R electrolyzer. After three-hour electrolysis, glycerol is selectively oxidized to glyceraldehyde with a turnover number (TON) of ≈1000 and Faradaic efficiency (FE) of 83 %. The cathode generated a stoichiometric amount of syngas with a CO:H2 ratio of 1.25±0.25 and an overall cobalt-based TON of 894 with a FE of 82 %. This prototype device inspires the design and implementation of nonconventional strategies for coupling CO2 R to less energy demanding, and value-added, oxidative chemistry

Feature similarity gradients detect alterations in the neonatal cortex associated with preterm birth

The early life environment programmes cortical architecture and cognition across the life course. A measure of cortical organisation that integrates information from multi-modal MRI and is unbound by arbitrary parcellations has proven elusive, which hampers efforts to uncover the perinatal origins of cortical health. Here, we use the Vogt-Bailey index to provide a fine-grained description of regional homogeneities and sharp variations in cortical microstructure based on feature gradients, and we investigate the impact of being born preterm on cortical development at term-equivalent age. Compared to term-born controls, preterm infants have a homogeneous microstructure in temporal and occipital lobes, and the medial parietal, cingulate, and frontal cortices, compared with term infants. These observations replicated across two independent datasets and were robust to differences that remain in the data after matching samples and alignment of processing and quality control strategies. We conclude that cortical microstructural architecture is altered in preterm infants in a spatially distributed rather than localised fashion.Keywords: feature similarity gradients, neonatal brain, preterm birth, MRI, neonatal corte

Visible-Light Flow Reactor Packed with Porous Carbon Nitride for Aerobic Substrate Oxidations.

A triphasic photocatalytic reactor employing a mesoporous carbon nitride photocatalyst and aerobic O2 was assembled to operate under continuous flow conditions. This reactor design allows for facile downstream processing and reusability in multiple flow cycles. The selective aerobic oxidation of alcohols and amines was chosen to demonstrate the applicability and performance advantage of this flow approach compared to that of conventional batch photochemistry. This precious-metal-free photocatalytic flow system operates under benign reaction conditions (visible light, low pressure, and mild temperature) and will stimulate the exploration of other oxidative reactions in a sustainable, scalable, and affordable manner

Operando film-electrochemical EPR spectroscopy tracks radical intermediates in surface-immobilized catalysts.

Acknowledgements: This study was supported by the Leverhulme Trust (grant no. RPG-2018-183 to M.M.R. and E.R.), a Leverhulme Early Career Fellowship (ECF-2021-072 to S.J.C.), the Isaac Newton Trust (20.08(r), to S.J.C.), an Imperial College President’s scholarship to Y.D., an EPSRC grant (EP/W005794/1) to M.M.R. and a UKRI Frontiers (ERC Advanced) grant (EP/X030563/1 to E.R.). The EPR measurements were performed at the Centre for Pulse EPR at Imperial College London (PEPR), supported by EPSRC grant no. EP/T031425/1 to M.M.R. We thank J. Eisermann (Imperial College) for using and improving the Laviron method fitting program. A. Collauto (Imperial College) and J. Eisermann are also acknowledged for helpful discussions.Funder: The Leverhulme Trust, Research Grant RPG-2018-183Funder: Imperial College President’s scholarshipThe development of surface-immobilized molecular redox catalysts is an emerging research field with promising applications in sustainable chemistry. In electrocatalysis, paramagnetic species are often key intermediates in the mechanistic cycle but are inherently difficult to detect and follow by conventional in situ techniques. We report a new method, operando film-electrochemical electron paramagnetic resonance spectroscopy (FE-EPR), which enables mechanistic studies of surface-immobilized electrocatalysts. This technique enables radicals formed during redox reactions to be followed in real time under flow conditions, at room temperature and in aqueous solution. Detailed insight into surface-immobilized catalysts, as exemplified here through alcohol oxidation catalysis by a surface-immobilized nitroxide, is possible by detecting active-site paramagnetic species sensitively and quantitatively operando, thereby enabling resolution of the reaction kinetics. Our finding that the surface electron-transfer rate, which is of the same order of magnitude as the rate of catalysis (accessible from operando FE-EPR), limits catalytic efficiency has implications for the future design of better surface-immobilized catalysts

Photoelectrochemical hybrid cell for unbiased CO2 reduction coupled to alcohol oxidation

The reduction of CO2 to renewable fuels must be coupled to a sustainable oxidation process to devise a viable solar fuel-producing device. In photoelectrochemical cells, water oxidation to O2 is the predominant oxidation reaction and typically requires a pair of light absorbers or an applied bias voltage when coupled to CO2 reduction. Here, we report a bias-free photoelectrochemical device for simultaneous CO2 reduction to formate and alcohol oxidation to aldehyde in aqueous conditions. The photoanode is constructed by co-immobilisation of a diketopyrrolopyrrole-based chromophore and a nitroxyl-based alcohol oxidation catalyst on a mesoporous TiO2 scaffold, providing a precious metal-free dye-sensitised photoanode. The photoanode was wired to a biohybrid cathode consisting of the CO2 reduction enzyme formate dehydrogenase integrated into a mesoporous indium tin oxide electrode. The bias-free cell delivers sustained photocurrents of up to 30 µA cm−2 under visible-light irradiation, resulting in simultaneous aldehyde and formate production. Our results show that single light absorber photoelectrochemical cells can be used for parallel fuel production and chemical synthesis from CO2 and waste streams in the absence of an external bias