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Metal nanoparticles, often supported on metal oxide promoters, are a cornerstone of heterogeneous catalysis. Experimentally, size effects are well-established and are manifested through changes to catalyst selectivity, activity and durability. Density Functional Theory (DFT) calculations have provided an attractive way to study these effects and rationalise the change in nanoparticle properties. However such computational studies are typically limited to smaller nanoparticles (approximately up to 50 atoms) due to the large computational cost of DFT. How well can such simulations describe the electronic properties of the much larger nanoparticles that are often used in practice? In this study, we use the ONETEP code, which is able to achieve more favourable computational scaling for metallic nanoparticles, to bridge this size gap. We present DFT calculations on entire Pd and Pd carbide nanoparticles of more than 300 atoms (approximately 2.5 nm diameter), and find major differences in the electronic structure of such large nanoparticles, in comparison to the commonly investigated smaller clusters. These differences are also manifested in the calculated chemical properties such as adsorption energies for C 2 H 2 , C 2 H 4 and C 2 H 6 on the pristine Pd and PdC x nanoparticles which are significantly larger (up to twice in value) for the ∼300 atoms structures. Furthermore, the adsorption of C 2 H 2 and C 2 H 4 on PdC x nanoparticles becomes weaker as more C is introduced in the Pd lattice whilst the impact of C concentration is also observed in the calculated reaction energies towards the hydrogenation of C 2 H 2 , where the formation of C 2 H 6 is hindered. Our simulations show that PdC x nanoparticles of about 5% C per atom fraction and diameter of 2.5 nm could be potential candidate catalysts of high activity in hydrogenation reactions. The paradigm presented in this study will enable DFT to be applied on similar sized metal catalyst nanoparticles as in experimental investigations, strengthening the synergy between simulation and experiment in catalysis., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Owing to the growing concerns about the dwindling fossil fuel reserves, increasing energy demand, and climate emergency, it is imperative to develop and deploy sustainable energy technologies to ensure future energy supply and to transition to the net-zero world. In this context, there is great potential in the biorefinery concept for supplying drop in biofuels in the form of biodiesel. Biodiesel as a fuel can certainly bridge the gap where electrification or the use of hydrogen is not feasible, for instance, in heavy vehicles and in the farm and marine transportation sectors. However, the biodiesel industry also generates a large amount of crude glycerol as the by-product. Due to the presence of several impurities, crude glycerol may not be a suitable feedstock for all high-value products derived from glycerol, but it fits well with glycerol esterification for producing glycerol acetins, which have numerous applications. This review critically looks at the processes using nanostructured solid/liquid acid catalysts for glycerol esterification, including the economic viability of the scale-up. The homogeneous catalysts reviewed herein include mineral acids and Brønsted acidic ionic liquids, such as SO 3 H-functionalized and heteropoly acid based ionic liquids. The heterogeneous catalysts reviewed herein include solid acid catalysts such as metal oxides, ion-exchange resins, zeolites, and supported heteropoly acid-based catalysts. Furthermore, the techno-economic analysis studies have shown the process to be highly profitable, confirming the viability of glycerol esterification as a potential tool for economic value addition to the biorefinery industry.

Fractures of the metacarpal particularly the 5th metacarpal is quite common among all hand fractures and has a high incidence in male adult population. Proper management of these fractures plays a key role in rehabilitation and early return to work thus reducing the economic burden. Treatment of these injuries depends on the type of injury: whether it is a closed/open fracture, degree of angulation at the fracture site and also mal-rotation and shortening of the finger. Non-operative management is suitable for fractures which are closed, non-displaced and without angulation or rotation. Open fractures, fractures with angulation and/or mal-rotation and fractures with neuro-vascular injury are more suitable for operative management. The acceptable angulation for conservative management for most studies is 70 degrees. Buddy strapping with a Futura splint provides good functional results. In fractures requiring operative intervention, K-wire fixation is a minimally invasive method of fixation, which in most cases has good functional results. Plate and screw fixation, however, is preferred for cases with significant comminution or multiple metacarpal fractures.

Sugarcane bagasse (SCB) is a significant agricultural residue generated by sugar mills based on sugarcane crop. Valorizing carbohydrate-rich SCB provides an opportunity to improve the profitability of sugar mills with simultaneous production of value-added chemicals, such as 2,3-butanediol (BDO). BDO is a prospective platform chemical with multitude of applications and huge derivative potential. This work presents the techno-economic and profitability analysis for fermentative production of BDO utilizing 96 MT of SCB per day. The study considers plant operation in five scenarios representing the biorefinery annexed to a sugar mill, centralized and decentralized units, and conversion of only xylose or total carbohydrates of SCB. Based on the analysis, the net unit production cost of BDO in the different scenarios ranged from 1.13 to 2.28 US$/kg, while the minimum selling price varied from 1.86 to 3.99 US$/kg. Use of the hemicellulose fraction alone was shown to result in an economically viable plant; however, this was dependent on the condition that the plant would be annexed to a sugar mill which could supply utilities and the feedstock free of cost. A standalone facility where the feedstock and utilities were procured was predicted to be economically feasible with a net present value of about 72 million US$, when both hemicellulose and cellulose fractions of SCB were utilized for BDO production. Sensitivity analysis was also conducted to highlight some key parameters affecting plant economics., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

The formation of interstitial PdC x nanoparticles (NPs) is investigated through DFT calculations. Insights on the mechanisms of carbidisation are obtained whilst the material's behaviour under conditions of increasing C-concentration is examined. Incorporation of C atoms in the Pd octahedral interstitial sites is occurring through the [111] facet with an activation energy barrier of 19.3-35.7 kJ mol -1 whilst migration through the [100] facet corresponds to higher activation energy barriers of 124.5-127.4 kJ mol -1 . Furthermore, interstitial-type diffusion shows that C will preferentially migrate and reside at the octahedral interstitial sites in the subsurface region with limited mobility towards the core of the NP. For low C-concentrations, migration from the surface into the interstitial sites of the NPs is thermodynamically favored, resulting in the formation of interstitial carbide. Carbidisation reaction energies are exothermic up to 11-14% of C-concentration and slightly vary depending on the shape of the structure. The reaction mechanisms turn to endothermic for higher concentration levels showing that C will preferentially reside on the surface making the interstitial carbide formation unfavorable. As experimentally observed, our simulations confirm that there is a maximum concentration of C in Pd carbide NPs opening the way for further computational investigations on the activity of Pd carbides in directed catalysis., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Glycerol acetins (mono-, di-, and tri) are produced via esterification with acetic acid. The acetins are commercially important industrial chemicals including their application as fuel additives, thus significant to environmental sustainability and economic viability of the biorefinery industry. Glycerol esterification with acetic acid was studied using partial tin exchanged tungstophosphoric acid supported on montmorillonite K-10 as catalysts. Partially exchanging the H + ion of DTP with Sn ( x = 1) increased the acidity of the catalyst and showed an increase in the catalytic activity as compared to the DTP/K-10 catalyst. A series of tin exchanged tungstophosphoric acid (20% w/w) supported on montmorillonite K-10 clay (Sn x -DTP/K-10, where x = 0.5-1.5) were synthesized and thoroughly characterized by using BET, XRD, FT-IR, UV-vis, and titration techniques. Among various catalysts, Sn 1 -DTP/K-10 was found to be the most active catalyst for glycerol esterification. Effects of different reaction parameters were studied and optimized to get high yields of glycerol triacetin. A suitable kinetic model of the reaction was fitted, and the Langmuir-Hinshelwood (L-H) dual-site model was able to describe the experimental data with high agreement between the experimental and calculated results. The prepared catalyst could be recycled at least four times without significant loss of activity. The overall process is green and environment friendly., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

Selective hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL) was studied using copper on manganese oxide octahedral molecular sieve (OMS-2) as catalysts. A range of copper supported on OMS-2 catalysts was prepared using the modified wet-impregnation technique and characterized thoroughly using powder X-ray diffraction, inductively coupled plasma optical emission spectroscopy metal analysis, Fourier transform infrared, high-resolution transmission electron microscopy and N 2 sorption analyses. Process parameters for selective hydrogenation of LA to GVL were optimized using the design of experiment (DoE) approach with response surface methodology comprising a central composite design. Using the optimized conditions (190°C reaction temperature, 20 bar H 2 pressure and 20 wt% Cu loading on OMS-2), up to 98% yield of GVL could be achieved in water as a solvent. Based on DoE, H 2 pressure had the most influence on GVL selectivity followed by catalyst loading used for the hydrogenation of LA. The response surface methodology model also showed synergistic effect of reaction temperature and H 2 pressure on the yield of GVL. 20 wt% Cu/OMS-2 catalysts were re-used up to four cycles and showed noticeable loss of activity after the first cycle due to observed leaching of loose Cu species, thereafter the activity loss diminished during subsequent recycles., (© 2022 The Authors.)

The effect of the sulfation of zirconia catalysts on their structure, acidity/basicity, and catalytic activity/selectivity toward the ketonization of organic acids is investigated by a combined experimental and computational method. Here, we show that, upon sulfation, zirconia catalysts exhibit a significant increase in their Brønsted and Lewis acid strength, whereas their Lewis basicity is significantly reduced. Such changes in the interplay between acid-base sites result in an improvement of the selectivity toward the ketonization process, although the measured conversion rates show a significant drop. We report a detailed DFT investigation of the putative surface species on sulfated zirconia, including the possible formation of dimeric pyrosulfate (S 2 O 7 2- ) species. Our results show that the formation of such a dimeric system is an endothermic process, with energy barriers ranging between 60.0 and 70.0 kcal mol -1 , and which is likely to occur only at high SO 4 2- coverages (4 S/nm 2 ), high temperatures, and dehydrating conditions. Conversely, the formation of monomeric species is expected at lower SO 4 2- coverages, mild temperatures, and in the presence of water, which are the usual conditions experienced during the chemical upgrading of biofuels., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

Nuclear magnetic resonance (NMR) and total neutron scattering techniques are established methods for the characterisation of liquid phases in confined pore spaces during chemical reactions. Herein, we describe the first combined total neutron scattering - NMR setup as a probe for the catalytic heterogeneous reduction of benzene-d6 with D2 in 3 wt% Pt/MCM-41.

Liquids under confinement exhibit different properties compared with their corresponding bulk phases, for example, miscibility, phase transitions, and diffusion. The underlying cause is the local ordering of molecules, which is usually only studied using pure simulation methods. Herein, we derive experimentally the structure of benzene confined in MCM-41 using total neutron scattering measurements. The study reveals a layering of molecules across a pore, and four concentric cylindrical shells can be distinguished for a pore with the radius of 18 Å. The nanoscale confinement of the liquid has a major effect on the spatial and orientational correlations observed between the molecules, when compared with the structure of the bulk liquid. These differences are most marked for molecules in parallel configurations, and this suggests differences in chemical reactivity between the confined and bulk liquids., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Aqueous liquid mixtures, in particular, those involving amphiphilic species, play an important role in many physical, chemical and biological processes. Of particular interest are alcohol/water mixtures; however, the structural dynamics of such systems are still not fully understood. Herein, a combination of terahertz time-domain spectroscopy (THz-TDS) and NMR relaxation time analysis has been applied to investigate 2-propanol/water mixtures across the entire composition range; while neutron diffraction studies have been carried out at two specific concentrations. Excellent agreement is seen between the techniques with a maximum in both the relative absorption coefficient and the activation energy to molecular motion occurring at ∼90 mol% H2O. Furthermore, this is the same value at which well-established excess thermodynamic functions exhibit a maximum/minimum. Additionally, both neutron diffraction and THz-TDS have been used to provide estimates of the size of the hydration shell around 2-propanol in solution. Both methods determine that between 4 and 5 H2O molecules per 2-propanol are found in the 2-propanol/water clusters at 90 mol% H2O. Based on the acquired data, a description of the structure of 2-propanol/water across the composition range is presented.

Stable chromium, molybdenum, tungsten, manganese, rhenium, ruthenium, osmium, cobalt, rhodium, and iridium metal nanoparticles (M-NPs) have been reproducibly obtained by facile, rapid (3 min), and energy-saving 10 W microwave irradiation (MWI) under an argon atmosphere from their metal-carbonyl precursors [M(x)(CO)(y)] in the ionic liquid (IL) 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIm][BF(4)]). This MWI synthesis is compared to UV-photolytic (1000 W, 15 min) or conventional thermal decomposition (180-250 degrees C, 6-12 h) of [M(x)(CO)(y)] in ILs. The MWI-obtained nanoparticles have a very small (<5 nm) and uniform size and are prepared without any additional stabilizers or capping molecules as long-term stable M-NP/IL dispersions (characterization by transmission electron microscopy (TEM), transmission electron diffraction (TED), and dynamic light scattering (DLS)). The ruthenium, rhodium, or iridium nanoparticle/IL dispersions are highly active and easily recyclable catalysts for the biphasic liquid-liquid hydrogenation of cyclohexene to cyclohexane with activities of up to 522 (mol product) (mol Ru)(-1) h(-1) and 884 (mol product) (mol Rh)(-1) h(-1) and give almost quantitative conversion within 2 h at 10 bar H(2) and 90 degrees C. Catalyst poisoning experiments with CS(2) (0.05 equiv per Ru) suggest a heterogeneous surface catalysis of Ru-NPs.