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This study investigates the cradle-to-gate life cycle assessment of four acrylic acid production routes. Acrylic acid, an important industrial chemical, is currently produced using fossil fuel-based propylene but it can be sustainably produced from biodiesel derived glycerol through different pathways that involve intermediates such as acrolein, allyl alcohol, or lactic acid. Environmental impacts, including global warming potential, water footprint, acidification, eutrophication, ozone layer depletion, photochemical smog, and human toxicity, are evaluated. Glycerol-based processes exhibit significant environmental impacts mainly due to the energy-intensive production of epichlorohydrin-derived glycerol. The total potential global warming for glycerol-based processes having intermediates allyl alcohol, lactic acid and acrolein, was 1.67 × 105, 1.80 × 105 and 1.34 × 105 kg CO2 eq. FU-1 respectively, with epichlorohydrinderived glycerol, whilst this value was 0.552 × 105 kg CO2 eq. FU-1 for the propylene-based process. However, changing the source of glycerol to purified crude glycerol from the biodiesel industry results in a considerable reduction of the environmental impact. A sensitivity analysis using the two-factor interaction (2FI) model showed that the global warming potential varies from 0.676 × 105 to 1.45 × 105 kg CO2 eq. FU-1 depending on the purification method used to purify crude glycerol and the glycerol content in the crude glycerol. It showed that a vacuum distillation purification process with 50% glycerol content had the least global warming values. This assessment provides insights into environmental performance trade-offs, guiding efforts towards more sustainable acrylic acid production and emphasizing the potential of using by-products from other industries to enhance the sustainability in chemical production processes. [ABSTRACT FROM AUTHOR]

Molecular transport is an important aspect in metal–organic frameworks (MOFs) as it affects many of their applications, such as adsorption/separation, drug delivery and catalysis. Yet probing the fundamental diffusion mechanisms in MOFs is challenging, and the interplay between the MOF's features (such as the pore structure and linker dynamics) and molecular transport remains mostly unexplored. Here, the pulsed-field gradient nuclear magnetic resonance (PFG NMR) technique is used to probe the diffusion of several probe molecules, i.e., water, xylenes and 1,3,5-triisopropylbenzene (TIPB), within the UiO-66 MOF and its derivatives (UiO-66NH2 and UiO-66Br). Exploiting differences in the size of probe molecules we were able to probe the diffusion rate selectively in the different pore environments of the MOFs. In particular, when relatively small molecules, such as water and small hydrocarbons, were used as probes, the PFG NMR log attenuation plots were non-linear with two distinctive diffusion regions, suggesting faster diffusion in the inter-crystalline space and slower diffusion within crystal aggregates, the latter occurring mostly inside the framework of the MOFs. Conversely, experiments with a larger probe molecule, i.e., TIPB, with a kinetic diameter of 0.95 nm, which makes it unable to access the framework windows of the MOF crystals, showed linear PFG NMR log attenuation plots, which indicates diffusion occurring in a single environment, most likely in the inter-crystalline space. Analysis of the apparent tortuosity values of the systems under investigation highlights the role of linker functionalisation in influencing the molecular diffusion of the probe molecules, which affects both intra-molecular interactions and pore accessibility within the MOF crystals. The findings of this work demonstrate that the diffusion behaviour of probe molecules within MOFs is influenced by the pore size, structure, functionalisation of the MOF linker and molecular interactions. Our study contributes to further advance the understanding of mass transport in MOFs by PFG NMR and provides insights that can inform the design and optimisation of MOF-based materials for various applications. [ABSTRACT FROM AUTHOR]

Alcohol oxidations are a key industrial chemical transformation, with aldehydes and ketones finding use in an array of applications. Nobel metals are known for their activity towards this chemoselective transformation, however, sustainable catalyst synthesis requires optimal utilisation of these scarce elements. Here, we report Au catalytic systems based on the deposition of isolated Au sites on different morphologies of ceria in which different surface facets of the support are exposed. Through tailoring the support morphology and from extensive catalyst characterisation, it is shown that the exposed facet is critical for controlling the formation (or not) of isolated Au sites. Both the 110 and 111 facets are capable of this feat, yielding single‐atom sites for rod, octahedron, and polyhedron morphologies. In contrast, the 100 facet is not, resulting in Au nanoparticles on cubic ceria. This dictation over Au species is critical to benzyl alcohol oxidation capacity at mild conditions and in the absence of a soluble base, with only single‐atom catalyst (SAC) systems demonstrating activity. Furthermore, the exposed surface facet also governs the degree of surface oxygen vacancies, which is critical to catalyst activity due to their control over substrate adsorption strength, as revealed through T1/T2 NMR relaxation measurements. [ABSTRACT FROM AUTHOR]

Within the realm of organic synthesis, photocatalysis has blossomed since the beginning of the last decade. A plethora of classical reactivities, such as selective oxidation of alcohol and amines, redox radical formation of reactive species in situ, and indirect activation of an organic substrate for cycloaddition by EnT, have been revised in a milder and more sustainable fashion via photocatalysis. However, even though the spark of creativity leads scientists to explore new reactions and reactivities, the urgency of replacing the toxic and critical metals that are involved as catalysts has encouraged chemists to find alternatives in the branch of science called organocatalysis. Unfortunately, replacing metal catalysts with organic analogues can be too expensive sometimes; however, this drawback can be solved by the reutilization of the catalyst if it is heterogeneous. The aim of this review is to present the recent works in the field of heterogeneous photocatalysis, applied to organic synthesis, enabled by continuous flow. In detail, among the heterogeneous catalysts, g-CN, polymeric photoactive materials, and supported molecular catalysts have been discussed within their specific sections, rather than focusing on the types of reactions. [ABSTRACT FROM AUTHOR]

The behaviour of multiple fluid phases within a porous medium is hard to predict. NMR measurements offer an excellent tool to probe such systems in a fast and non-invasive way. Such systems can be relevant to hydrocarbon recovery, catalysis, and CO2 and H2 geo-storage, among others. Since electrolyte solutions are always present in subsurface reservoirs, understanding their behaviour within porous media is highly important. In this study, we use NMR relaxation and diffusion methods to investigate the diffusion coefficients and strength of interactions between alumina surfaces and brines at various NaCl concentrations, focusing on the effect of salt concentration on transport and interactions within the porous structure. Furthermore, we study the spontaneous displacement of dodecane, a model hydrocarbon, from the same alumina pellets using the same brine solutions. Results show that brines of lower salinity consistently displace more dodecane in total, after soaking dodecane-saturated pellets in a brine solution for several days. This indicates that increased salt concentrations can reduce wettability towards the aqueous phase in simple metal oxide surfaces and highlights the capabilities of NMR to efficiently study such systems. [ABSTRACT FROM AUTHOR]

Chemical activated carbons (PET‐H2SO4 and PET‐KOH) were prepared from post‐consumer polyethylene terephthalate (PET) wastes using pyrolysis under moderate reaction temperatures by changing pyrolysis time and chemical activating agents. The produced carbons were characterized and tested in adsorption reactions of manganese, chromium, and cobalt ions in aqueous solutions. Results showed a high percentage removal of these inorganic ions from water: 98 % for Mn2+, 87 % for Cr3+, and 88 % for Co2+. Freundlich isotherms gave a better fit to the experimental data obtained with good correlation coefficient values in the range of 0.99‐1 compared to other isotherms. The pseudo‐second order kinetic model best described the chemical adsorption process as an exchange of electrons between the carbon and inorganic ions in solutions. The diffusion models showed that the process is controlled by a multi‐kinetic stage adsorption process. In summary, this work demonstrates that the production of activated carbon from PET waste bottles is a potential alternative to commercial activated carbon and can be considered a sustainable waste management technology for removing these non‐biodegradable plastic wastes from the environment. [ABSTRACT FROM AUTHOR]

The tobacco waste generated from the tobacco agriculture and industry, including the discarded stem and leaf, often needs dehydration pretreatment before thermal conversion utilization. In order to study the water activity and migration of tobacco waste during the pretreatment process, TG-NMR (Thermogravimetric Nuclear Magnetic Resonance) was used to obtain the drying curves and LF-NMR (Low Field Nuclear Magnetic Resonance) T2 inversion spectrum at each stage of tobacco drying. Meanwhile, the variation pattern of pore distribution during the dehydration process of two types of tobacco waste has been obtained. Combined with the pore distribution changes, a possible spatial migration mode of water was proposed. The change of adsorption energy of water during tobacco drying was calculated, and verified the above hypothesis. This study results provide reference for the optimization of dehydration pretreatment process for different tobacco waste in order to reduce energy consumption during recycling of tobacco biomass. [ABSTRACT FROM AUTHOR]

Photoreforming of lignocellulose biomass is widely recognised as a challenging but key technology for producing value‐added chemicals and renewable hydrogen (H2). In this study, H2 production from photoreforming of organosolv lignin in a neutral aqueous solution was studied over a 0.1 wt % Pt/TiO2 (P25) catalyst with ultraviolet A (UVA) light. The H2 production from the system employing the lignin (~4.8 μmol gcat−1 h−1) was comparable to that using hydroxylated/methoxylated aromatic model compounds (i. e. guaiacol and phenol, 4.8–6.6 μmol gcat−1 h−1), being significantly lower than that from photoreforming of cellulose (~62.8 μmol gcat−1 h−1). Photoreforming of phenol and reaction intermediates catechol, hydroquinone and benzoquinone were studied to probe the mechanism of phenol oxidation under anaerobic photoreforming conditions with strong adsorption and electron transfer reactions lowering H2 production from the intermediates relative to that from phenol. The issues associated with catalyst poisoning and low photoreforming activity of lignins demonstrated in this paper have been mitigated by implementing a process by which the catalyst was cycled through anaerobic and aerobic conditions. This strategy enabled the periodic regeneration of the photocatalyst resulting in a threefold enhancement in H2 production from the photoreforming of lignin. [ABSTRACT FROM AUTHOR]

CO2 utilization is an important process in the chemical industry with great environmental power. In this work we show how CO2 and H2 can be reacted to form methanol on an iron(II) center and highlight the bottlenecks for the reaction and what structural features of the catalyst are essential for efficient turnover. The calculations predict the reactions to proceed through three successive reaction cycles that start with heterolytic cleavage of H2 followed by sequential hydride and proton transfer processes. The H2 splitting process is an endergonic process and hence high pressures will be needed to overcome this step and trigger the hydrogenation reaction. Moreover, H2 cleavage into a hydride and proton requires a metal to bind hydride and a nearby source to bind the proton, such as an amide or pyrazolyl group, which the scorpionate ligand used here facilitates. As such the computations highlight the non‐innocence of the ligand scaffold through proton shuttle from H2 to substrate as an important step in the reaction mechanism. [ABSTRACT FROM AUTHOR]

Stabilisation of metal species using hydroxyl‐rich dealuminated zeolites is a promising method for catalysis. However, insights into the interactions between the hydroxyl groups in zeolite and noble metals and their effects on catalysis are not yet fully understood. Herein, comparative studies were conducted using Pt catalysts supported on hydroxyl‐rich dealuminated Beta (deAl‐Beta) and the pristine proton‐form Beta (H‐Beta) for catalytic oxidation of toluene. The findings suggest that during impregnation the Pt precursor (i. e., Pt(NH3)4(NO3)2) interacted with different sites on deAl‐Beta and H‐Beta, leading to the formation of supported Pt nanoparticles with different physicochemical properties. In detail, for H‐Beta, the Pt precursor interacted with Al‐OH and isolated external Si‐OH sites, yielding Pt NPs with a higher Pt0 proportion of ~71 % compared to ~57 % Pt0 on deAl‐Beta. Comparatively, abundant hydroxyl groups on deAl‐Beta such as silanol nest and isolated internal Si‐OH stabilised highly active Pt‐O species. The resulting Pt/deAl‐Beta exhibited improved activity and anti‐coking ability than Pt/H‐Beta in catalytic toluene oxidation. For example, the temperature for 50 % toluene conversion was 193 °C for Pt/deAl‐Beta vs. 232 °C for Pt/H‐Beta, and the coke deposition was 1.7 % vs. 6.7 % (after the 24‐h longevity test), respectively. According to the toluene‐temperature programmed desorption (toluene‐TPD), 1H nuclear magnetic resonance (1H NMR) relaxation and in situ diffuse reflection Fourier transform spectroscopy (in situ DRIFTS) characterisation, the enhanced performance of Pt/deAl‐Beta could be ascribed to (i) the active Pt‐O sites stabilised by hydroxyl groups, which interact with toluene easily for conversion, and (ii) the acid‐free feature of the deAl‐Beta support, which avoids the formation of coke precursors (such as benzoate species) on the catalyst surface. Findings of the work can serve as the design guidelines for making effective supported metal catalysts using zeolitic carriers. [ABSTRACT FROM AUTHOR]

The manipulation of carbon nitride (CN) structures is one main avenue to enhance the activity of CN‐based photocatalysts. Increasing the efficiency of photocatalytic heterogeneous materials is a critical step toward the realistic implementation of sustainable schemes for organic synthesis. However, limited knowledge of the structure/activity relationship in relation to subtle structural variations prevents a fully rational design of new photocatalytic materials, limiting practical applications. Here, the CN structure is engineered by means of a microwave treatment, and the structure of the material is shaped around its suitable functionality for Ni dual photocatalysis, with a resulting boosting of the reaction efficiency toward many CX (X = N, S, O) couplings. The combination of advanced characterization techniques and first‐principle simulations reveals that this enhanced reactivity is due to the formation of carbon vacancies that evolve into triazole and imine N species able to suitably bind Ni complexes and harness highly efficient dual catalysis. The cost‐effective microwave treatment proposed here appears as a versatile and sustainable approach to the design of CN‐based photocatalysts for a wide range of industrially relevant organic synthetic reactions. [ABSTRACT FROM AUTHOR]

Heterogenisation of homogeneous catalysts onto solid supports represents a potential strategy to make the homogeneous catalytic function recyclable and reuseable. Yet, it is usually the case that immobilised catalysts have much lower catalytic activity than their homogeneous counterpart. In addition, the presence of a solid interface introduces a higher degree of complexity by modulating solid/fluid interactions, which can often influence adsorption properties of solvents and reactive species and, ultimately, catalytic activity. In this work, the influence of support and solvent in the H-transfer reduction of propionaldehyde over Al(OiPr)3–SiO2, Al(OiPr)3–TiO2 and Al(OiPr)3–Al2O3 heterogenised catalysts has been studied. Reaction studies are coupled with both NMR relaxation measurements as well as molecular dynamics (MD) simulations in order to unravel surface and solvation effects during the reaction. The results show that, whilst the choice of the support does not influence significantly catalytic activity, reactions carried out in solvents with high affinity for the catalyst surface, or able to hinder access to active sites due to solvation effects, have a lower activity. MD calculations provide key insights into bulk solvation effects involved in such reactions, which are thought to play an important role in determining the catalytic behaviour. The activity of the heterogenised catalysts was found to be comparable with that of the homogeneous Al(OiPr)3 catalysts for all supports used, showing that for the type of reaction studied immobilisation of the homogeneous catalyst onto solid supports is a viable, robust and effective strategy. [ABSTRACT FROM AUTHOR]

Supported Au colloidal nanoparticles have been prepared in the presence of stabilising polymers, such as, PVA, PVP and PEG (polyvinylalcohol, polyvinylpyrrolidone, polyethylene glycol). The effect of the polymer to Au weight ratio was investigated, for the synthesis of Au nanoparticles with varying particle size and particle size distribution. By varying the polymer/Au wt/wt ratio, Au nanoparticles with mean diameters from 3 to 8 nm were synthesised. The synthesised Au catalysts were studied in the liquid phase oxidation of glucose to glucaric acid under alkaline conditions. We demonstrated that the choice of polymer and polymer to Au weight ratio, have an important influence in terms of catalytic activity and yield to glucaric acid. The highest yield to glucaric acid (22%) was obtained using Au–PVA catalysts. A strong deactivation was observed using Au catalysts. Further evaluation of the possible reasons for deactivation were investigated using experimental, computational and NMR relaxation studies. [ABSTRACT FROM AUTHOR]

Organocatalyst immobilization onto solid supports represents a promising method for enabling asymmetric organocatalysis while retaining the advantages of heterogeneous catalysts, including catalyst separation, recycling, and the use of fixed‐bed reactors. Understanding how such heterogenized catalytic systems work is fundamental to develop and tailor more efficient ones. Herein, we have elucidated the role of reactant molecular structure on surface interactions and reactivity for asymmetric aldol reactions between benzaldehyde derivatives and hydroxyacetone catalyzed by SBA‐15 immobilized L‐proline. NMR relaxation time analysis reveals that a stronger interaction between the aldehyde and the catalyst surface reduces catalytic reactivity, which is attributed to reduced access of hydroxyacetone to the L‐proline surface sites, hence inhibiting the formation of the enamine intermediate between hydroxyacetone and L‐proline. The results show that surface phenomena in these systems are important considerations for reactant selection, opening up new directions to explore in this area of research. [ABSTRACT FROM AUTHOR]

[Display omitted] • The effect of reducing agent on SCR of NO x over Ag/Al 2 O 3 catalyst was studied. • Alcohols give better performances than aliphatic and aromatic hydrocarbons. • NMR T 1 / T 2 measurements show that alcohols have higher surface affinity for the catalyst. • A correlation between NMR T 1 / T 2 measurements and reaction activation temperature is established. • Adsorption properties of reducing agents over the catalyst are important in determining the SCR catalyst activity. NMR relaxation has been used to characterise the strength of surface interaction of reducing agent species in Ag/Al 2 O 3 catalysts used for the selective catalytic reduction (SCR) of NO x. Several classes of compounds, including aliphatic and aromatic hydrocarbons, as well as alcohols, were investigated. The results show that the strength of interaction of the reducing agent with the catalyst surface, characterised by the NMR relaxation time ratio T 1 / T 2 , plays an important role in determining the catalyst performances, with reducing agents able to compete with water for adsorption over the surface giving better catalytic activities. In particular, a clear trend was observed when comparing the T 1 / T 2 ratio of different reducing agents with the initial activity of the catalyst, in particular with the activation temperature, with species such as alcohols, which showed a higher affinity with the catalyst, showing an easier initial activation. Whilst SCR is a complex reaction, whereby a series of phenomena are responsible for the overall catalytic activity, the strength of surface interaction of the reducing agent is a useful indicator for the initial catalytic activation in such processes. [ABSTRACT FROM AUTHOR]

The relative surface affinities of pyridine within microporous HZSM-5 zeolites are explored using twodimensional ¹H nuclear magnetic resonance (NMR) relaxation time measurements. The dimensionless ratio of longitudinal-to-transverse nuclear spin relaxation times T1/T2 is shown to exhibit strong sensitivity to the silica/alumina ratio (SAR) of these zeolites, which is indicative of material acidity. This trend is interpreted in terms of increased pyridine surface affinity with decreasing SAR. Temperature programmed desorption (TPD) analysis corroborates this observation, revealing a distinct increase in the heat of desorption associated with adsorbed pyridine as a function of decreasing SAR. A direct correlation between NMR and TPD data suggests NMR relaxation time analysis can be a valuable tool for the non-invasive characterisation of adsorption phenomena in microporous solids. [ABSTRACT FROM AUTHOR]