The reduction of water has been achieved through a non-noble-metal-based homogeneous catalyst system that is formed in situ. Optimisation of the ligand quantities increased catalyst turnover numbers compared to preformed complexes. Mechanistic studies confirm a heteroleptic Cu complex as the active photosensitiser (PS) and an in situ formed Fe-phosphido dimer complex as the water reduction catalyst. The in situ method has been used to screen a range of ligands for the active PS, which has led to the identification a number of structural features important to longevity and performance.
Shale hydration is the main reason causing wellbore instability in oil and gas drilling operations. In this study, nanoscale laponite as a shale inhibitor was employed to stabilize wellbores. The inhibition property of laponite suspensions was evaluated by an immersion experiment, linear swelling measurement, and a shale recovery test. Then the shale inhibition mechanism was studied by using capillary suction time (CST) measurement, a thixotropy study, plugging performance evaluation, and related theoretical analysis. Evaluation experiment results showed that laponite had a better inhibition property than widely used inhibitors of potassium chloride (KCl) and poly(ester amine) (PA). The mechanism study revealed that integration of several factors strengthened the inhibition property of laponite suspensions. Laponite nanoparticles could plug interlayer spaces of clays by electrostatic interaction to reduce water invasion; the "house of cards" structure of laponite suspensions enables large CST values and low free water contents; the excellent thixotropy of a laponite nanofluid could allow a nanofilm to form in order to reduce water invasion into the formation; the nanoscale laponite particles could substantially reduce the shale permeability and form less porous surfaces. Furthermore, laponite could considerably decrease the filtrate volume of the drilling fluid, while KCl and PA had negative influences on the properties of the drilling fluid. This approach described herein might provide an avenue to inhibit shale hydration.
A series of phenanthroline-based ligands have been synthesised and their influence as bidentate nitrogen ligands in heteroleptic [Cu(P^P)(N^N)] photosensitisers in light-driven water reduction has been studied. In this noble-metal-free Cu-Fe-based photocatalytic water reduction system, the structural effects of the nitrogen ligands have been explored, including the steric and electronic effects of substituents at the 2,9- and 4,7-positions of phenanthroline. Ligands were prepared that led to increased hydrogen generation, with turnover numbers (TON ) of up to 1388 being observed. All the new complexes were electrochemically and photophysically characterised. We demonstrate for the first time that the presence of fluorine in nitrogen ligands increases the efficacy of copper complexes in photocatalytic hydrogen production.
An organocatalytic domino thia-Michael/ aldol condensation reaction of a, b-unsaturated aldehydes with 1, 4-dithiane-2,5-diol catalyzed by chiral diphenylprolinol TMS ether has been developed, which provides a new practical and direct route to chiral dihydrothiophenes with high yields (up to 90%) and excellent enantioselectivities (up to > 99% ee). The catalytic mechanism of the domino reaction was further confirmed through the APCI-MS detection of proposed reaction intermediates.
Asymmetric Michael addition reactions of unmodified ketones to nitroalkenes were performed in PEGs catalyzed by novel pyrrolidinyl-thioimidazolium salts to give products in up to 97% yield and 99% enantioselectivity; ESI mass spectrometric detection for the first time gave evidence of the presence of the PEG-organocatalyst host-guest complex.
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