This study presents the proof-of-principle and sensitivity analysis of a dual-bed catalytic system achieving exceptional acrylic acid yield (up to 67.2 %) from glycerol oxi-dehydration - among the highest reported in the literature. A systematic investigation was carried out to boost the catalytic performance by investigating several variables, including type of catalysts, reaction parameters, and bed configurations. The reaction process involved the dehydration of glycerol to acrolein over HZSM-5 zeolites, followed by further oxidation to acrylic acid using vanadium-molybdenum mixed oxide catalysts having orthogonal (Ortho-MoVO) or amorphous structure (AmorMoVO). HZSM-5 zeolites with Si/Al ratios ranging from 23 to 500 were evaluated in the presence and absence of air at 280 degrees C for the glycerol dehydration, with HZSM-5 (200) showing optimal performance. The dual-bed configuration (HZSM-5/MoVO) significantly outperformed the mixed-bed system, with Amor-MoVO achieving the highest yield of 67.2 % at 280 degrees C. When using Ortho-MoVO under optimized conditions (280 degrees C, 4972 h- 1 GHSV, oxygen-to-glycerol ratio of 9.5), the system maintained a high acrylic acid yield of 58.8 %. The superior performance of the dual-bed system was attributed to the spatial separation of reaction zones, enabling controlled oxygen exposure and minimizing undesired oxidation pathways. The main by-products from the oxidehydration reaction in the dual-bed system were acetic acid, propanoic acid, formic acid and COx, however, additional by-products such as acetaldehyde, propanal and acrolein were observed in the case of the mixed-bed system. This study demonstrates the feasibility of a promising route for the sustainable acrylic acid production from renewable feedstocks, with a perspective on industrial implementation.

In recent decades, surplus crude glycerol has been generated in large amounts as a waste product of biodiesel production, leading to bottlenecks in the supply chain of the biodiesel industry. This waste glycerol represents an important potential renewable feedstock and platform chemical; however, its purification is often needed for further processing. Advancements towards glycerol purification are being made using sustainable purification techniques aimed at improving the biodiesel industry's environmental footprint. Many studies focussing on various techniques to purify glycerol can be found in the literature; however, very few studies to evaluate the environmental impacts of the purification processes have been reported. This paper provides a critical investigation on the cradle-to-gate life cycle assessment (LCA) of three different processes for purifying crude glycerol, namely, physicochemical treatment and membrane purification (PMP) processes, vacuum distillation purification (VDP) processes and ion exchange purification (IEP) processes having a functional unit (FU) of 1000 kg of purified glycerol. These purification processes were modelled using Aspen plus software v12.1 in combination with Super Pro Designer v13. CCaLC2 (Carbon Calculations over the Life Cycle of Industrial Activities) was used to measure the environmental impacts associated with each process. By following the ISO 14044:2006 methodology and utilising the CCaLC2 tool, seven different types of potential environmental impacts have been investigated, which include carbon footprint, water footprint, acidification, eutrophication, ozone layer depletion, photochemical smog and human toxicity. Sensitivity analysis of the LCA was carried out using the response surface method (RSM) to determine the most effective parameter within the LCA. The total carbon footprint of the PMP, VDP and IEP processes are 3466.82, 1745.72 and 2239.71 kg CO2 eq. FU-1 respectively. The LCA study determined that waste generated as a result of crude glycerol impurities from the three processes had one of the highest environmental impacts on the overall process. For the PMP and IEP processes, the raw materials used in the physicochemical treatment also contribute significantly to the carbon footprint and other environmental impacts. Lastly, aspects concerning the environmental impacts from the PMP glycerol purification process have been addressed by analysing the raw materials from different sources accompanied by altered waste disposal methods (i.e. the incineration of generated wastes as opposed to landfilling) in an attempt to reduce the overall environmental impacts. For the PMP process, which has the highest carbon footprint, usage of differently sourced raw materials and altered waste disposal treatments resulted in 39% reduction in total carbon footprint and 54% reduction in the total ozone layer depletion. Sensitivity analysis of the LCA shows that the glycerol content within the crude glycerol was the most significant parameter.

5-(hydroxymethyl)furfural (HMF) is a key biomass derived platform chemical used to produce fuel precursors or additives and value-added chemicals, synthesised by the cascade isomerisation of glucose and subsequent dehydration of reactively formed fructose to HMF over Lewis and Bronsted acid catalysts, respectively. Zirconia is a promising catalyst for such reactions; however, the impact of acid properties of different zirconia phases is poorly understood. In this work, we unravel the role of the zirconia crystalline phase in glucose isomerisation and fructose dehydration to HMF. The Lewis acidic monoclinic phase of zirconia is revealed to preferentially facilitate glucose isomerisation, while the nanoparticulate tetragonal phase possesses Brønsted acid sites which favour fructose dehydration. Synergy between both zirconia phases facilitates cascade HMF production, with both catalysts investigated as physical mixtures in batch and flow reactor configurations. Using a physical mixture of only 15 wt % m- ZrO 2 with 85 wt % t- ZrO 2 in either batch or packed bed reactor configuration is sufficient to reach equilibrium conversion of glucose for subsequent dehydration by the t- ZrO 2 component. Under continuous flow, a six-fold increase in HMF production was obtained when operating with a physical mixture of m- and t- ZrO 2 compared to that from a single bed of t- ZrO 2.

Sustainable production of acrylic acid can be achieved through various glycerol conversion routes. In this review, we discuss the strategies, challenges and prospects for the utilisation of waste glycerol as an alternative feedstock.

Herein, the alcoholysis of furfuryl alcohol in a seriesof SBA-15-pr-SO3H catalysts with different pore sizes isreported. Elementalanalysis and NMR relaxation/diffusion methods show that changes inpore size have a significant effect on catalyst activity and durability.In particular, the decrease in catalyst activity after catalyst reuseis mainly due to carbonaceous deposition, whereas leaching of sulfonicacid groups is not significant. This effect is more pronounced inthe largest-pore-size catalyst C3, which rapidly deactivatesafter one reaction cycle, whereas catalysts with a relatively mediumand small average pore size (named, respectively, C2 and C1) deactivate after two reaction cycles and to a lesser extent.CHNS elemental analysis showed that C1 and C3 experience a similar amount of carbonaceous deposition, suggestingthat the increased reusability of the small-pore-size catalyst canbe attributed to the presence of SO3H groups mostly presenton the external surface, as corroborated by results on pore cloggingobtained by NMR relaxation measurements. The increased reusabilityof the C2 catalyst is attributed to a lower amount ofhumin being formed and, at the same time, reduced pore clogging, whichhelps to maintain accessible the internal pore space.

Impact of stabilisers on the catalytic performance of supported Au colloidal nanoparticles for the liquid phase oxidation of glucose to glucaric acid.

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.

Sn and Ga doped zeolite Y catalysts were tested for the isomerization of glucose to fructose carried out in different solvents (water, methanol and ethanol). Therein, ethanol favoured a Lewis acid site catalyzed pathway that promotes glucose isomerization to fructose, whereas methanol resulted in an equal distribution of products (mannose, fructose and alkyl fructoside). In contrast, the catalysts were totally inactive in water solvent. NMR relaxation measurements, including solvent displacement experiments, suggested that the lack of catalytic activity in water is due to the strong adsorption of this solvent within the zeolite pores blocking reactants from the Lewis acid sites active for the sugar isomerization. In comparison, ethanol adsorbs relatively more strongly than methanol, so is retained in the pores where solvated fructose is preferentially prevented from the further reaction on Brønsted acid sites situated outside of the pore. NMR relaxation measurements using pyridine and tetrahydrofuran (THF) and pyridine-DRIFTS measurements suggest metal doping had little effect on the overall relative acid strength of the zeolites but resulted in zeolites with increased Lewis acid strength relative to the non-doped zeolites. The results reported provide direct experimental evidence on the importance of adsorption properties of solvents within zeolites used for glucose to fructose isomerization and may serve as a starting point for a new approach towards designing and optimizing such catalytic systems.

The depletion of fossil resources is driving the research towards renewable alternatives, like lignocellulosic biomass. Therefore, the development of efficient continuous-flow processes, allowing to achieve better productivity compared to batch processes, will play a crucial role in promoting a sustainable transition. In this context, we report on the continuous-flow, gas-phase, catalytic transfer hydrogenation (CTH) of methyl levulinate and ethanol over zirconia catalysts, in particular focusing on the effect of two different crystalline phases (i.e. monoclinic, m-ZrO2, and tetragonal, t-ZrO2) on catalyst performance. An in-depth catalyst characterisation was coupled with both computational and H-1 NMR relaxation studies to assess the structure-activity relationship, providing fundamental insights into the catalytic process and future catalyst optimization. The results, indicate that the higher Lewis acidity and basicity along with the lower affinity with ethanol of m-ZrO2 with respect to t-ZrO2 are responsible for the promotion of undesired oligomerisation reactions of angelica lactones responsible for catalyst deactivation.

In this paper we carry out a surface study of promising supported solid acid catalysts commonly used for the production of high value chemicals derived from glycerol. In particular, gamma, theta and alpha alumina (Al2O3) were modified by (i) grafting with 5 wt% zirconia, (ii) doping with 30 wt% silicotungstic acid (STA), and (iii) using both zirconia and STA. The aim is to rationalise the effect of these different parameters on structural properties and surface adsorption through a comprehensive multi-technique approach, including recently developed NMR relaxation techniques. XRD and laser Raman spectroscopy confirmed a strong interaction between STA and the gamma-/theta-Al2O3 resulting in a distortion of the supported STA Keggin structure relative to that of bulk STA. Conversely, a much weaker interaction between the supported STA and alpha-Al2O3 was measured. NMR relaxation demonstrated that the STA doping increases the adsorption properties of the catalyst, particularly for gamma-/theta-Al2O3. For catalysts based on alpha-Al2O3, such effect was negligible. Thermogravimetric/differential thermogravimetry (TGA/DTG) analysis suggested that zirconia-grafted and non-grafted theta-Al2O3 and gamma-Al2O3 are suitable materials for increasing the thermal stability of STA whereas alpha-Al2O3 (both grafted and non-grafted) does not improve the thermal stability of STA.

The surface chemistry and morphology of biochars produced by pyrolysis of walnut shells affects their utility for adsorption applications. Yet, little is known about surface interactions in the pores of these materials, mostly due to the challenging nature of accessing information at this length scale in a non-destructive manner. Here, for the first time, the relative adsorption strengths of solvents comprising different functional groups to internal (pore) surfaces of walnut shells and derived biochars were investigated using low-field nuclear magnetic resonance (NMR) relaxation time measurements to non-destructively probe interactions of fluids with pore surfaces. Carbon bonding state compositions of these materials with respect to distance from the particle surface were determined using X-ray photoelectron spectroscopy coupled with ion beam etching. Alkaline pretreatment was found to increase the hydrophilicity of both walnut shells and derived biochars. It was found to increase surface interactions with hydroxyl groups, and to decrease those with methyl groups. Results were contextualised by thermogravimetric analysis, scanning electron microscopy, and previous in-situ X-ray imaging results. Taken together, results showed that alkaline pretreatment may be used to modulate responses to pyrolysis temperature of several factors that affect adsorption properties including surface hydrophilicity, particle size, porosity, pore accessibility, and surface texture.

In this study, we use zeolite Y as a support for the synthesis of Sn and Ga doped zeolites aimed at the isomerization of glucose to fructose. Though these materials are inactive in water, they are active in methanol and we could ascertain a reaction pathway involving a hydride shift for the interconversion of glucose to fructose and mannose, and a Brønsted acid pathway with the formation of a methyl fructoside intermediate and its hydrolysis to fructose if water was added afterwards. By using characterizations comprising: chemisorption, XPS, XRD, HAADF-STEM and EXAFS; it was possible to demonstrate that a straightforward impregnation protocol for the preparation of our catalysts, led to Sn/Y mainly consisting of small SnO2 clusters on the external surface of the zeolite, whereas Ga/Y consisting of highly dispersed Ga species mostly inside the zeolite pores; and a catalytic activity that appears to be dominated by Brønsted acid sites.

The behaviour of solvents in solid-supported proline organocatalysts is explored using NMR relaxation measurements coupled with reaction screening. Solvents with a lower affinity for the solid surface lead to a higher reactivity.

In this work, we applied low-field, NMR spin-lattice measurements to evaluate for the first time the effect of carbonization temperature (range 600-1000.) on the preparation of Alumina-Carbon Molecular Sieve Membranes (Al-CMSMs), providing new insights into intra-pore fluid interactions. The results show that the average Al-CMSM pore size generally increases with carbonization temperature whilst the hydrophilicity of the pore surface, and the amount of strongly adsorbed H2O, decreases with an increasing carbonization temperature. As such, lower carbonization temperatures produce more hydrophilic membranes, with further evidence provided by FTIR measurements demonstrating the presence of polar functional groups on the surface, with water interacting more strongly with the membrane surface, as evidenced by NMR. It was found that the Al-CMSM carbonization temperature significantly affected permeance and H2O/CH4 permselectivity by altering the membrane pore size distribution and pore hydrophilicity. H2O permeance values are seen to be up to 100 times larger than respective CH4 permeance values. The greater permeance of H2O is attributed to the larger kinetic diameter of CH4 relative to H2O and the adsorption of water in the hydrophilic pores enhancing the adsorption-diffusion transport mechanism. Optimal water permeation temperatures are thus higher for the more hydrophilic membranes, obtained at lower carbonization temperatures, as more energy is required to remove strongly adsorbed water blocking the pores. At higher carbonization temperatures, the Knudsen diffusion mechanism of permeance dominates over the adsorption-diffusion mechanism thereby reducing permeance as diffusion slows due to collisions between gas molecules and the pore walls. CH4 permeation always occurs via Knudsen diffusion with CH4 permeance increasing with permeation temperature due to the increased rate of CH4 diffusion.

Solvent effects in homogeneous catalysis are known to affect catalytic activity. Whilst these effects are often described using qualitative features, such as Kamlet-Taft parameters, experimental tools able to quantify and reveal in more depth such effects have remained unexplored. In this work, PFG NMR diffusion and T-1 relaxation measurements have been carried out to probe solvent effects in the homogeneous catalytic reduction of propionaldehyde to 1-propanol in the presence of aluminium isopropoxide catalyst. Using data on diffusion coefficients it was possible to estimate trends in aggregation of different solvents. The results show that solvents with a high hydrogen-bond accepting ability, such as ethers, tend to form larger aggregates, which slow down the molecular dynamics of aldehyde molecules, as also suggested by T-1 measurements, and preventing their access to the catalytic sites, which results in the observed decrease of catalytic activity. Conversely, weakly interacting solvents, such as alkanes, do not lead to the formation of such aggregates, hence allowing easy access of the aldehyde molecules to the catalytic sites, resulting in higher catalytic activity. The work reported here is a clear example on how combining traditional catalyst screening in homogeneous catalysis with NMR diffusion and relaxation time measurements can lead to new physico-chemical insights into such systems by providing data able to quantify aggregation phenomena and molecular dynamics.

The favorable exploitation of carbon nitride (CN) materials in photocatalysis for organic synthesis requires the appropriate fine-tuning of the CN structure. Here, we present a deep investigation of the structure/activity relationship of CN in the photocatalytic perfluoroalkylation of organic compounds. Four types of CN bearing subtle structural differences were studied via conventional characterization techniques and innovative nuclear magnetic resonance (NMR) experiments, correlating the different structures with the fundamental mechanistic nexus and especially highlighting the importance of the halogen bond strength between the reagent and the catalyst surface. The optimum catalyst exhibited an excellent performance, with a very wide reaction scope, and could prominently trigger the model reaction using natural sunlight. The work lays a platform for establishing a new approach in the development of heterogeneous photocatalysts for organic synthesis related to medical, agricultural, and material chemistry.

•Diffusion of glycerol in nanopores is determined by the degree of pore saturation.•Contradictory experimental results are due to lack of control of the degree of pore saturation.•Molecular dynamics and NMR experiments confirm enhanced mobility of glycerol in nanopores.•Solid-liquid and liquid-vapour interfaces determine the disruption of the H-bond network.

The aim of this work is to develop and quantify the tuning of transport properties in porous catalytic materials by tailoring their textural properties. In order to do this, alumina catalyst carriers were prepared from boehmite by varying preparation conditions to produce carriers with different pore sizes and macropore content. Pore size and macropore content decreased with boehmite mixing time and increased with calcination temperature due to alumina phase transformations occurring. Mass transport within the different materials was studied by pulsed-field gradient NMR diffusion techniques, with a low-field, bench-top NMR instrument, using n-octane as the probe molecule. The diffusion results revealed that mass transport occurs more readily in carriers with greater pore size and macropore content, by providing a comprehensive and quantitative description of this behaviour. In particular, up to a pore size of 17.0 nm diffusion increases very rapidly with pore size; at pore sizes greater than 17.0 nm and macropore content greater than 27% the major geometrical restrictions imposed by the pore structure on the probe molecule were removed and the diffusivity of guest molecules reaches a constant plateau, suggesting that a pore size greater than 17.0 nm and a macropore content greater than 27% do not lead to significant further improvements in mass transport properties. Diffusion studies using water, methanol and ethanol, as probe molecules with functional hydroxyl groups able to interact with the surface, showed that in samples with small pores and no amount of macropores, surface interactions of these guest molecules with the pore surface have a significant effect on determining the diffusive motion, in addition to the effect of the physical pore structure. For larger pores and larger macropore content, the surface chemistry of the pore walls has a much smaller impact on the diffusive motion inside the porous matrix. This work gives a comprehensive and quantitative overview on how to tailor carrier preparation procedures in order to tune mass transport, providing a rational guideline with important implications in design, preparation and applications of porous materials.