The air tolerant precatalyst, [Rh­(L)­(NBD)]Cl ([1]­Cl) [L = κ3-( i Pr2PCH2CH2)2NH, NBD = norbornadiene], mediates the selective synthesis of N-methylpolyaminoborane, (H2BNMeH) n , by dehydropolymerization of H3B·NMeH2. Kinetic, speciation, and DFT studies show an induction period in which the active catalyst, Rh­(L)­H3 (3), forms, which sits as an outer-sphere adduct 3·H 3 BNMeH 2 as the resting state. At the end of catalysis, dormant Rh­(L)­H2Cl (2) is formed. Reaction of 2 with H3B·NMeH2 returns 3, alongside the proposed formation of boronium [H2B­(NMeH2)2]­Cl. Aided by isotopic labeling, Eyring analysis, and DFT calculations, a mechanism is proposed in which the cooperative “PNHP” ligand templates dehydrogenation, releasing H2BNMeH (ΔG ‡ calc = 19.6 kcal mol–1). H2BNMeH is proposed to undergo rapid, low barrier, head-to-tail chain propagation for which 3 is the catalyst/initiator. A high molecular weight polymer is formed that is relatively insensitive to catalyst loading (M n ∼71 000 g mol–1; Đ, of ∼ 1.6). The molecular weight can be controlled using [H2B­(NMe2H)2]Cl as a chain transfer agent, M n = 37 900–78 100 g mol–1. This polymerization is suggested to arise from an ensemble of processes (catalyst speciation, dehydrogenation, propagation, chain transfer) that are geared around the concentration of H3B·NMeH2. TGA and DSC thermal analysis of polymer produced on scale (10 g, 0.01 mol % [1]­Cl) show a processing window that allows for melt extrusion of polyaminoborane strands, as well as hot pressing, drop casting, and electrospray deposition. By variation of conditions in the latter, smooth or porous microstructured films or spherical polyaminoboranes beads (∼100 nm) result.

Metal organic framework UiO-66 is studied as an adaptable heterogeneous catalyst for glucose conversion. UiO-66 was modified by; i) partial linker substitution, ii) particle size modulation and iii) linker defects. We studied the effect of crystallinity and functional groups on the glucose conversion and product yields. The main products are: i) fructose from the isomerisation of glucose, ii) mannose from the epimerisation of glucose and iii) 5-hydroxymethyl furfural from the dehydration of fructose. We found that defective and nano crystalline UiO-66 catalyst performs best for isomerisation. When 50 % of the linkers of UiO-66 are replaced by a sulfonate-containing linker, the catalyst shows higher isomerisation activity than other UiO-66 catalysts. Naphthalene-dicarboxylate linkers were introduced to induce hydrophobicity and this catalyst further increased isomerisation activity showing 31 % fructose selectivity. Finally, the promising catalysts were tested in a flow reactor and a bifunctional mixed linker catalyst possessing both hydrophobic and acidic functional groups is shown to be stable in a time-onstream study.

with a useful lifetime of decades. Tin perovskites also offer narrower bandgaps than their lead analogues, enabling a greater proportion of the solar spectrum to be harvested. [4] The Achilles' heel of tin perovskites for PV applications is their higher susceptibility to oxidation in air which stems from the tendency of Sn 2+ to convert to the more thermodynamically stable +4 oxidation state upon exposure to ambient air. [5] The intrinsic resistance of the device stack to air ingress dictates the degree of packaging required for practical applications, and thus the packaging cost, so there is a need to identify ways to make tin perovskite PVs more intrinsically stable. [1,2] Strategies to achieving this goal include making the perovskite more stable by compositional engineering or defect passivation [6] and/or making the other

The composition of atmospheric aerosols varies with time, season, location, and environment. This affects key aerosol properties such as hygroscopicity and reactivity, influencing the aerosol’s impact on the climate and air quality. The organic fraction of atmospheric aerosol emissions often contains surfactant material, such as fatty acids. These molecules are known to form three-dimensional nanostructures in contact with water. Different nanostructures have marked differences in viscosity and diffusivity that are properties whose understanding is essential when considering an aerosol’s atmospheric impact. We have explored a range of nanostructures accessible to the organic surfactant oleic acid (commonly found in cooking emissions), simulating variation that is likely to happen in the atmosphere. This was achieved by changing the amount of water, aqueous phase salinity and by addition of other commonly coemitted compounds: sugars and stearic acid (the saturated analogue of oleic acid). The nanostructure was observed by both synchrotron and laboratory small/wide angle X-ray scattering (SAXS/WAXS) and found to be sensitive to the proxy composition. Additionally, the spacing between repeat units in these nanostructures was water content dependent (i.e., an increase from 41 to 54 Å in inverse hexagonal phase d-spacing when increasing the water content from 30 to 50 wt %), suggesting incorporation of water within the nanostructure. A significant decrease in mixture viscosity was also observed with increasing water content from ∼104 to ∼102 Pa s when increasing the water content from 30 to 60 wt %. Time-resolved SAXS experiments on levitated droplets of this proxy confirm the phase changes observed in bulk phase mixtures and demonstrate that coexistent nanostructures can form in droplets. Aerosol compositional and subsequent nanostructural changes could affect aerosol processes, leading to an impact on the climate and urban air pollution.

A novel continuous flow process for selective hydrogenation of α, β-unsaturated aldehyde (cinnamaldehyde, CAL) to the unsaturated alcohol (cinnamyl alcohol, COL) has been reported in a tube reactor coated with a Pt/SiO 2 catalyst. A 90% selectivity towards the unsaturated alcohol was obtained at the aldehyde conversion of 98.8%. This is a six-fold improvement in the selectivity compared to a batch process where acetals were the main reaction products. The increased selectivity in the tube reactor was caused by the suppression of acid sites responsible for the acetal formation after a short period on stream in the continuous process. In a fixed bed reactor, it had a similar acetal suppression phenomenon but showed lower product selectivity of about 47-72% due to mass transfer limitations. A minor change in selectivity and conversion caused by product inhibition was observed during the 110 h on stream with a turnover number (TON) reaching 3000 and an alcohol production throughput of 0.36 kg g Pt −1 day −1 in the single tube reactor. The catalysts performance after eight reaction cycles was fully restored by calcination in air at 400 • C. The tube reactors provide an opportunity for process intensification by increasing the reaction rates by a factor of 2.5 at the reaction temperature of 150 • C compared to 90 • C with no detrimental effects on catalyst stability or product selectivity.

Fluoro-polyacrylic acid block copolymers with vary narrow dispersity are shown to have sub-2 nm domain sizes on phase separation.

We show that particle size, morphology, nanocrystallinity, surface area, and defect density of (Y,Eu)VO4 structures can be tuned by one-pot colloidal conversion of rare earth hydroxycarbonates in water/ethylene glycol (EG)...

The structure and molecular order in the thermotropic ionic liquid crystal (ILC), [choline][geranate(H)octanoate], an analogue of Choline And GEranate (CAGE), which has potential for use as a broad-spectrum antimicrobial and transdermal and oral delivery agent, were investigated by magic-angle spinning (MAS) nuclear magnetic resonance (NMR), polarizing optical microscopy, small-angle X-ray scattering (SAXS), and mass spectrometry. Mass spectrometry and the 1 H NMR chemical shift reveal that CAGE-oct is a dynamic system, with metathesis (the exchange of interacting ions) and hydrogen exchange occurring between hydrogen-bonded/ionic complexes such as [(choline)(geranate)(H)(octanoate)], [(choline)(octanoate) 2 (H)], and [(choline)-(geranate) 2 (H)]. These clusters, which are shown by mass spectrometry to be significantly more stable than expected for typical electrostatic ion clusters, involve hydrogen bonding between the carboxylic acid, carboxylate, and hydroxyl groups, with rapid hydrogen bond breaking and re-formation observed to average the 1 H chemical shifts. The formation of a partial bilayer liquid crystal (LC) phase was identified by SAXS and polarizing optical microscopy at temperatures below ∼293 K. The occurrence of this transition close to room temperature could be utilized as a potential temperature-induced "switch" of the anisotropic properties for particular applications. The presence of an isotropic component of approximately 23% was observed to coexist with the LC phase, as detected by polarizing optical microscopy and quantified by both 1 H− 13 C dipolar-chemical shift correlation (DIPSHIFT) and 1 H double-quantum (DQ) MAS NMR experiments. At temperatures above the LC-to-isotropic transition, intermediate-range order (clustering of polar and nonpolar domains), a feature of many ILs, persists. Site-specific order parameters for the LC phase of CAGE-oct were obtained from the MAS NMR measurement of the partially averaged 13 C− 1 H dipolar couplings (D CH ) by cross-polarization (CP) build-up curves and DIPSHIFT experiments, and 1 H− 1 H dipolar couplings (D HH ) by double-quantum (DQ) build-up curves. The corresponding order parameters, S CH and S HH , are in the range 0−0.2 and are lower compared to those for smectic (i.e., layered) phases of conventional nonionic liquid crystals, resembling those of lamellar phases formed by lyotropic surfactant−solvent systems.