Route For Production Research Articles

Recent Research in Solar-Driven Hydrogen Production

Climate concerns require immediate actions to reduce the global average temperature increase. Renewable electricity and renewable energy-based fuels and chemicals are crucial for progressive de-fossilization. Hydrogen will be part of the solution. The main issues to be considered are the growing market for H2 and the “green” feedstock and energy that should be used to produce H2. The electrolysis of water using surplus renewable energy is considered an important development. Alternative H2 production routes should be using “green” feedstock to replace fossil fuels. We firstly investigated these alternative routes through using bio-based methanol or ethanol or ammonia from digesting agro-industrial or domestic waste. The catalytic conversion of CH4 to C and H2 was examined as a possible option for decarbonizing the natural gas grid. Secondly, water splitting by reversible redox reactions was examined, but using a renewable energy supply was deemed necessary. The application of renewable heat or power was therefore investigated, with a special focus on using concentrated solar tower (CST) technology. We finally assessed valorization data to provide a tentative view of the scale-up potential and economic aspects of the systems and determine the needs for future research and developments.

Combined Effect of Particle Reinforcement and T6 Heat Treatment on the Compressive Deformation Behavior of an A357 Aluminum Alloy at Room Temperature and at 350 °C

Solid state sintering of cast aluminum powders by resistance heating sintering (RHS), also known as spark plasma sintering or field-assisted sintering technique, creates a very fine microstructure in the bulk material. This leads to high performance material properties with an improved strength and ductility compared to conventional production routes of the same alloys. In this study, the mechanical behavior of an RHS-sintered age-hardenable A357 (AlSi7Mg0.6) cast alloy and a SiCp/A357 aluminum matrix composite (AMC) was investigated. Aiming for high strength and good wear behavior in tribological applications, the AMC was reinforced with a high particle content (35 vol.%) of a coarse particle fraction (d50 = 21 µm). Afterwards, separated and combined effects of particle reinforcement and heat treatment were studied under compressive load both at room temperature and at 350 °C. At room temperature compression, the strengthening effect of precipitation hardening was about twice as high as that for the particle reinforcement, despite the high particle content. At elevated temperatures, the compressive deformation behavior was characterized by simultaneously occurring temperature-activated recovery, recrystallisation and precipitation processes. The occurrence and interaction of these processes was significantly affected by the initial material condition. Moreover, a rearrangement of the SiC reinforcement particles was detected after hot deformation. This rearrangement lead to a homogenized dispersion of the reinforcement phase without considerable particle fragmentation, which offers the potential for secondary thermo-mechanical processing of highly reinforced AMCs.

Efficient electrocatalytic nitrate reduction using 3D copper foam-supported Co hexagonal nanoparticles in a membrane electrode assembly

Electrocatalytic nitrate reduction reaction (NO3RR) provides a promising route for nitrate recycling and ammonia production. In this work, Co nanoparticle catalyst was developed on a copper foam substrate (CoNPs/CF) by electrodeposition. The CoNPs/CF catalysis exhibits a Faradaic efficiency (FE) of 92.0% at −0.2 V vs. RHE and an NH3 yield rate of 14328.65 μg h−1 cm−2 at −0.5 V vs. RHE. In-suit Raman spectroscopy and theoretical calculations demonstrated that the 3D copper foam structure of the substrate enhances the electron exchange capacity, which promotes the adsorption of nitrate on the cobalt (Co) surface. Moreover, Membrane Electrode Assembly (MEA) is employed with CoNPs/CF, contributing to 98.43 mg h−1 with FE over 80%. Coupled with an air stripping process, this configuration has enabled the successful production of high-purity gaseous NH3 products. This work suggests a practical and viable approach for the conversion of wastewater nitrate into valuable ammonia products.

Highly Efficient Electrosynthesis of Glycine over an Atomically Dispersed Iron Catalyst.

Glycine is a nonessential amino acid that plays a vital role in various biological activities. However, the conventional synthesis of glycine requires sophisticated procedures or toxic feedstocks. Herein, we report an electrochemical pathway for glycine synthesis via the reductive coupling of oxalic acid and nitrate or nitrogen oxides over atomically dispersed Fe-N-C catalysts. A glycine selectivity of 70.7% is achieved over Fe-N-C-700 at -1.0 V versus RHE. Synergy between the FeN3C structure and pyrrolic nitrogen in Fe-N-C-700 facilitates the reduction of oxalic acid to glyoxylic acid, which is crucial for producing glyoxylic acid oxime and glycine, and the FeN3C structure could reduce the energy barrier of *HOOCCH2NH2 intermediate formation thus accelerating the glyoxylic acid oxime conversion to glycine. This new synthesis approach for value-added chemicals using simple carbon and nitrogen sources could provide sustainable routes for organonitrogen compound production.

Tricoordinated Single-Atom Cobalt in Zeolite Boosting Propane Dehydrogenation.

Propane dehydrogenation (PDH) reaction has emerged as one of the most promising propylene production routes due to its high selectivity for propylene and good economic benefits. However, the commercial PDH processes usually rely on expensive platinum-based and poisonous chromium oxide based catalysts. The exploration of cost-effective and ecofriendly PDH catalysts with excellent catalytic activity, propylene selectivity, and stability is of great significance yet remains challenging. Here, we discovered a new active center, i.e., an unsaturated tricoordinated cobalt unit (≡Si-O)CoO(O-Mo) in a molybdenum-doped silicalite-1 zeolite, which afforded an unprecedentedly high propylene formation rate of 22.6 molC3H6 gCo-1 h-1 and apparent rate coefficient of 130 molC3H6 gCo-1 h-1 bar-1 with >99% of propylene selectivity at 550 °C. Such activity is nearly one magnitude higher than that of previously reported Co-based catalysts in which cobalt atoms are commonly tetracoordinated, and even superior to that of most of Pt-based catalysts under similar operating conditions. Density functional theory calculations combined with the state-of-the-art characterizations unravel the role of the unsaturated tricoordinated Co unit in facilitating the C-H bond-breaking of propane and propylene desorption. The present work opens new opportunities for future large-scale industrial PDH production based on inexpensive non-noble metal catalysts.

Effect of post-processing and variation of the building angle of Ti-6Al-4 V disks obtained by selective laser melting: A comparison of physical, chemical and mechanical properties to machined disks

Additive Manufacturing (AM) is driving the development of dental implants with freedom of design, material savings, and predictable properties. The modification of a single parameter, and post-processing treatments affects the final macro and microstructure. The aim was to evaluate the effect of changing the building angle, using the Selective Laser Melting (SLM) technique, on the physical, chemical, and mechanical properties and to compare them with sanded manufacturing surfaces and machined surfaces, with and without chemical surface treatment. There were 8 groups of Ti-6Al-4 V discs (Ø 10 mm×2 mm), classified as machined (M), machined with acid-alkali treatment (TM), SLM 0° (AM0), SLM 0° with sanding (SAM0), SLM 45° (AM45), SLM 45° with sanding (SAM45), SLM 90° (AM90), and SLM 90° with sanding (SAM90). The tests used were Scanning Electron Microscopy (SEM), Energy Dispersive X-ray Spectroscopy (EDS), roughness, wettability, surface free energy, X-ray diffraction (XRD), and Vickers hardness. The normality of the data was checked using the Shapiro-Wilk test followed by Kruskal-Wallis and ANOVA, with Dunn and Tukey post-tests, with a significance level of 5%. SEM revealed angle dependence in the number of unmelted powder particles and topographical heterogeneity, and EDS reported the elemental composition of the base alloy. AM90 showed the highest wettability among the manufactured groups, and the chemical surface treatment increased the wettability of the machined sample (p<0.001). In the roughness analysis, the higher the building angle, the higher the surface roughness . Sanding provided homogeneity in roughness, wettability, surface free energy, and microhardness. It was concluded that the production routes, change in angle, sanding and surface treatment affect the macro and microstructure of titanium surfaces. Changing the building angle influenced all of the topographical characteristics of the material, a parameter that can be changed and improved that is important for determining properties.

Neurotensin (8-13) and Neuromedin N Neuropeptides Radiolabelling with Copper-64 Produced on Solid or Liquid Targets.

On the verge of a theranostic approach to personalised medicine, copper-64 is one of the emerging radioisotopes in nuclear medicine due to its exploitable nuclear and biochemical characteristics. The increased demand for copper-64 for preclinical and clinical studies has prompted the development of production routes. This research aims to compare the (p,n) reaction on nickel-64 solid versus liquid targets and evaluate the effectiveness of [64Cu]CuCl2 solutions prepared by the two routes. As new treatments for neurotensin receptor-overexpressing tumours have developed, copper-64 was used to radiolabel Neurotensin (8-13) and Neuromedin N. High-quality [64Cu]CuCl2 solutions were prepared using ACSI TR-19 and IBA Cyclone Kiube cyclotrons. The radiochemical purity after post-irradiation processing reached 99% (LT) and 99.99% (ST), respectively. The irradiation of a solid target with 11.8 MeV protons and 150 μAh led to 704 ± 84 MBq/μA (17.6 ± 2.1 GBq/batch at EOB). At the end of the purification process (1 h, 90.90% activity yield), the solution for peptide radiolabelling had a radioactive concentration of 1340.4 ± 70.1 MBq/mL (n.d.c.). The irradiation of a liquid target with 16.9 MeV protons and 230 μAh resulted in 3.7 ± 0.2 GBq/batch at EOB, which corresponds to an experimental production yield of 6.89 GBq.cm3/(g.µA)sat. Benefiting from a shorter purification process (40 min), the activity yielded 90.87%, while the radioactive concentration of the radiolabelling solution was lower (492 MBq/mL, n.d.c.). The [64Cu]CuCl2 solutions were successfully used for the radiolabelling of DOTA-NT(8-13) and DOTA-NN neuropeptides, resulting in a high RCP (>99%) and high molar activity (27.2 and 26.4 GBq/μmol for LT route compared to 45 and 52 GBq/μmol for ST route, respectively). The strong interaction between the [64Cu]Cu-DOTA-NT(8-13) and the colon cancerous cell lines HT29 and HCT116 proved that the specificity for NTR had not been altered, as shown by the uptake and retention data.

Bipolar membrane crystallization enables near zero-waste production of high-purity oxalic acid crystals

The sodium formate method is currently the predominant route for oxalic acid production but is environmentally harmful. Water splitting in bipolar membranes provides the possibility for clean production of oxalic acid. However, bipolar membrane electrodialysis(BMED) also suffers from the major drawbacks of low concentrations and low purity products. Herein, we propose the use of bipolar membrane crystallization (BMC) to achieve synergistic conversion and crystallization of oxalic acid dihydrate. The dissolution of oxalate in aqueous solution and the electromigration of oxalate through the membrane were precisely tuned under different current densities. The consecutive electromigration of oxalate could boost the dissolution of oxalate. The morphology of the H2C2O4·H2O crystals is related to the current density: a plate-like shape is obtained at 5 mA/cm2, while a needle-shaped crystal is obtained at 10 mA/cm2. The intermittent crystallization of five batches of BMC demonstrated the robustness of bipolar membrane crystallization for the near zero-waste production of oxalic acid.

155Tb production by cyclotrons: what level of 155Gd enrichment allows clinical applications?

Background155Tb represents a potentially useful radionuclide for diagnostic medical applications, but its production remains a challenging problem, in spite of the fact that many production routes have been already investigated and tested. A recent experimental campaign, conducted with low-energy proton beams impinging on a 155Gd target with 91.9% enrichment, demonstrated a significant co-production of 156gTb, a contaminant of great concern since its half-life is comparable to that of 155Tb and its high-energy γ emissions severely impact on the dose released and on the quality of the SPECT images. In the present investigation, the isotopic purity of the enriched 155Gd target necessary to minimize the co-production of contaminant radioisotopes, in particular 156gTb, was explored using various computational simulations.ResultsStarting from the recent experimental data obtained with a 91.9% 155Gd-enriched target, the co-production of other Tb radioisotopes besides 155Tb has been theoretically evaluated using the Talys code. It was found that 156Gd, with an isotopic content of 5.87%, was the principal contributor to the co-production of 156gTb. The analysis also demonstrated that the maximum amount of 156Gd admissible for 155Tb production with a radionuclidic purity higher than 99% was 1%. A less stringent condition was obtained through computational dosimetry analysis, suggesting that a 2% content of 156Gd in the target can be tolerated to limit the dose increase to the patient below the 10% limit. Moreover, it has been demonstrated that the imaging properties of the produced 155Tb are not severely affected by this level of impurity in the target.Conclusions155Tb can be produced with a quality suitable for medical applications using low-energy proton beams and 155Gd-enriched targets, if the 156Gd impurity content does not exceed 2%. Under these conditions, the dose increase due to the presence of contaminant radioisotopes remains below the 10% limit and good quality images, comparable to those of 111In, are guaranteed.

Tetrametallic mastery: Cluster-doped graphdiyne as a superior electrocatalyst for hydrogen evolution

Hydrogen evolution reaction (HER) is a promising route for sustainable hydrogen production. However, its efficiency is limited by kinetic barriers. Herein, we employ density functional theory (DFT) calculations to demonstrate a new strategy of embedding tetrametallic transition metal clusters (3TM1-TM2) into the pores of graphdiyne (GDY) to effectively optimize its HER performance. By screening 900 configurations, 10 prototypes displayed near-ideal hydrogen adsorption free energies. Among them, 3W–Hg@GDY with a ΔGH of −0.00035 eV was identified as the optimal candidate. Analysis of the electronic structure reveals hybridization between the metal d orbitals and GDY p orbitals near the Fermi level, creating partially filled impurity states to promote hydrogen adsorption. Additionally, coordination between the three TM1 atoms and active TM2 atom in the cluster enables precise tuning of TM2's electron density to achieve a moderate interaction with the adsorbed H, facilitating superior HER catalysis. Our findings showcase a new paradigm of cluster engineering for modulating GDY's reactivity that holds great promise as a universal approach for the design of high-performance GDY-based electrocatalysts beyond HER.

Engineering Pseudomonas putida KT2440 for Dipicolinate Production via the Entner-Doudoroff Pathway.

Dipicolinic acid (DPA), a cyclic diacid, has garnered significant interest due to its potential applications in antimicrobial agents, antioxidants, chelating reagents, and polymer precursors. However, its natural bioproduction is limited since DPA is only accumulated in Bacillus and Clostridium species during sporulation. Thus, heterologous production by engineered strains is of paramount importance for developing a sustainable biological route for DPA production. Pseudomonas putida KT2440 has emerged as a promising host for the production of various chemicals thanks to its robustness, metabolic versatility, and genetic tractability. The dominant Entner-Doudoroff (ED) pathway for glucose metabolism in this strain offers an ideal route for DPA production due to the advantage of NADPH generation and the naturally balanced flux between glyceraldehyde-3-phosphate and pyruvate, which are both precursors for DPA synthesis. In this study, DPA production via the ED pathway was in silico designed in P. putida KT2440. The systematically engineered strain produced dipicolinate with a titer of 11.72 g/L from glucose in a 5 L fermentor. This approach not only provides a sustainable green route for DPA production but also expands our understanding of the metabolic potential of the ED pathway in P. putida KT2440.

Boosting hydrogen production from alkaline water splitting by regulating interlayer stress via lattice mismatch in NiS/MoS2

Alkaline water splitting currently represents one of the most promising routes for sustainable hydrogen production. However, the key challenge with this method lies in the development of low-cost catalysts showing high-performance for hydrogen evolution reaction (HER). Given the rapid advances in the structural design of HER catalysts, a potential procedure to boost their performance is introduced herein. A controllable interlayer stress is generated at the homojunction NiS/NiS interface of electrodeposited hybrid transition metal sulphide NiS/MoS2, by precisely regulating lattice mismatches of NiS nanostructures, achieve a precise control over its charge transfer resistance and the effective balance of electrochemical area. Accordingly, an optimal design, NM5030 (NiS(50 mA/cm2)-NiS(20 mA/cm2)/MoS2/CC), showing an excellent HER performance in alkaline electrolyte is produced. It can drive a high current density of 10 mA/cm2, 100 mA/cm2 and 400 mA/cm2 at a low overpotential of 18 mV, 93 mV and 161 mV, respectively. Under chronoamperometric test, no obvious reduction in current density is observed after 48 h, indicating its high stability. Overall, this work demonstrates the feasibility and effectiveness of the strategy of fabricating lattice mismatch to find an optimal layered structure based catalyst for efficient HER.

Inhibition of urease-mediated ammonia production by 2-octynohydroxamic acid in hepatic encephalopathy

Hepatic encephalopathy is a neuropsychiatric complication of liver disease which is partly associated with elevated ammonemia. Urea hydrolysis by urease-producing bacteria in the colon is often mentioned as one of the main routes of ammonia production in the body, yet research on treatments targeting bacterial ureases in hepatic encephalopathy is limited. Herein we report a hydroxamate-based urease inhibitor, 2-octynohydroxamic acid, exhibiting improved in vitro potency compared to hydroxamic acids that were previously investigated for hepatic encephalopathy. 2-octynohydroxamic acid shows low cytotoxic and mutagenic potential within a micromolar concentration range as well as reduces ammonemia in rodent models of liver disease. Furthermore, 2-octynohydroxamic acid treatment decreases cerebellar glutamine, a product of ammonia metabolism, in male bile duct ligated rats. A prototype colonic formulation enables reduced systemic exposure to 2-octynohydroxamic acid in male dogs. Overall, this work suggests that urease inhibitors delivered to the colon by means of colonic formulations represent a prospective approach for the treatment of hepatic encephalopathy.

Technoeconomic and Emissions Analysis of the Hybrid Redox Process for the Production of Acetic Acid with CO2 Utilization

AbstractThe production of oxygenated hydrocarbons, such as acetic acid, using captured CO2 is a promising pathway to reduce greenhouse gas emissions in the chemical industry. The use of a chemical looping‐based hybrid redox process (HRP) is proposed to convert CO2 and natural gas into separate CO and syngas streams that can be used to produce various commodity oxygenates, while allowing the beneficial utilization of captured CO2. Here, a detailed technoeconomic analysis of HRP applied to the production of acetic acid is presented. Emissions and energy analyses show the ability of HRP to lower the CO2 emissions for acetic acid synthesis by 74% compared to a conventional steam and autothermal reforming route. HRP also offers a potential 34% reduction in capital costs. Compared to a dry reforming based acetic acid production route, HRP has the potential for significantly lower costs. If integrated with a low carbon energy source, HRP has the potential to achieve a negative emission of greenhouse gas (‐0.50 kg CO2 per kg acetic acid).

COF/In2S3 S-Scheme Photocatalyst with Enhanced Light Absorption and H2O2-Production Activity and fs-TA Investigation.

Photocatalytic hydrogen peroxide (H2O2) synthesis from water and O2 is an economical, eco-friendly, and sustainable route for H2O2 production. However, single-component photocatalysts are subjected to limited light-harvesting range, fast carrier recombination, and weak redox power. To promote photogenerated carrier separation and enhance redox abilities, an organic/inorganic S-scheme photocatalyst is fabricated by in situ growing In2S3 nanosheets on a covalent organic framwork (COF) substrate for efficient H2O2 production in pure water. Interestingly, compared to unitary COF and In2S3, the COF/In2S3 S-scheme photocatalysts exhibit significantly larger light-harvesting range and stronger visible-light absorption. Partial density of state calculation, X-ray photoelectron spectroscopy, and femtosecond transient absorption spectroscopy reveal that the coordination between In2S3 and COF induces the formation of mid-gap hybrid energy levels, leading to smaller energy gaps and broadened absorption. Combining electron spin resonance spectroscopy, radical-trapping experiments, and isotope labeling experiments, three pathways for H2O2 formation are identified. Benefited from expanded light-absorption range, enhanced carrier separation, strong redox power, and multichannel H2O2 formation, the optimal composite shows an impressive H2O2-production rate of 5713.2µmol g-1 h-1 in pure water. This work exemplifies an effective strategy to ameliorate COF-based photocatalysts by building S-scheme heterojunctions and provides molecular-level insights into their impact on energy level modulation.

Think global act local: The dependency of global lithium-ion battery emissions on production location and material sources

The pursuit of low-carbon transport has significantly increased demand for lithium-ion batteries. However, the rapid increase in battery manufacturing, without adequate consideration of the carbon emissions associated with their production and material demands, poses the threat of shifting the bulk of emissions upstream. In this article, a life cycle assessment (LCA) model is developed to account for the cradle-to-gate carbon footprint of lithium-ion batteries across 26 Chinese provinces, 20 North American locations and 19 countries in Europe and Asia. Analysis of published LCA data reveals significant uncertainty associated with the carbon emissions of key battery materials; their overall contribution to the carbon footprint of a LIB varies by a factor of ca. 4 depending on production route and source. The links between production location and the gate-to-gate carbon footprint of battery manufacturing are explored, with predicted median values ranging between 0.1 and 69.5 kg CO2-eq kWh−1. Leading western-world battery manufacturing locations in the US and Europe, such as Kentucky and Poland are found to have comparable carbon emissions to Chinese rivals, even exceeding the carbon emissions of battery manufacturing in several Chinese provinces. Such resolution on material and energy contributions to the carbon footprint of LIBs is essential to inform policy- and decision-making to minimise the carbon emissions of the battery value chain. Given the current status quo, the global carbon footprint of the lithium-ion battery industry is projected to reach up to 1.0 Gt CO2-eq per year within the next decade. With material supply chain decarbonisation and energy savings in battery manufacturing, a lower estimate of 0.5 Gt CO2-eq per year is possible.

The efficient synthesis and purification of 2'3'- cGAMP from Escherichia coli.

Agonists of the stimulator of interferon genes (STING) pathway are being explored as potential immunotherapeutics for the treatment of cancer and as vaccine adjuvants for infectious diseases. Although chemical synthesis of 2'3' - cyclic Guanosine Monophosphate-Adenosine Monophosphate (cGAMP) is commercially feasible, the process results in low yields and utilizes organic solvents. To pursue an efficient and environmentally friendly process for the production of cGAMP, we focused on the recombinant production of cGAMP via a whole-cell biocatalysis platform utilizing the murine cyclic Guanosine monophosphate-Adenosine monophosphate synthase (mcGAS). In E. coli BL21(DE3) cells, recombinant expression of mcGAS, a DNA-dependent enzyme, led to the secretion of cGAMP to the supernatants. By evaluating the: (1) media composition, (2) supplementation of divalent cations, (3) temperature of protein expression, and (4) amino acid substitutions pertaining to DNA binding; we showed that the maximum yield of cGAMP in the supernatants was improved by 30% from 146 mg/L to 186 ± 7 mg/mL under optimized conditions. To simplify the downstream processing, we developed and validated a single-step purification process for cGAMP using anion exchange chromatography. The method does not require protein affinity chromatography and it achieved a yield of 60 ± 2 mg/L cGAMP, with <20 EU/mL (<0.3 EU/μg) of endotoxin. Unlike chemical synthesis, our method provides a route for the recombinant production of cGAMP without the need for organic solvents and supports the goal of moving toward shorter, more sustainable, and more environmentally friendly processes.

Influence of Defects and Charges on the Colloidal Stabilization of Graphene in Water.

Mastering graphene preparation is an essential step to its integration into practical applications. For large-scale purposes, full graphite exfoliation appears as a suitable route for graphene production. However, it requires overpowering attractive van der Waals forces demanding large energy input, with the risk of introducing defects in the material. This difficulty can be overcome by using graphite intercalation compounds (GICs) as starting material. The greater inter-sheet separation in GICs (compared with graphite) allows the gentler exfoliation of soluble graphenide (reduced graphene) flakes. A solvent exchange strategy, accompanied by the oxidation of graphenide to graphene, can be implemented to produce stable aqueous graphene dispersions (Eau de graphene, EdG), which can be readily incorporated into many processes or materials. In this work, we prove that electrostatic forces are responsible for the stability of fully exfoliated graphene in water, and explore the influence of the oxidation and solvent exchange procedures on the quality and stability of EdG. We show that the amount of defects in graphene is limited if graphenide oxidation is carried out before exposing the material to water, and that gas removal of water before the incorporation of pre-oxidized graphene is advantageous for the long-term stability of EdG.

Modelling assessment of resource competition for renewable basic chemicals and the effect of recycling

AbstractThis work assesses pathways towards a net‐zero greenhouse gas (GHG) emissions chemical industry sector in Germany until 2050, focusing on the ammonia, methanol, ethylene and adipic acid subsectors and the effect of the recycling of C embedded in chemical end products on the GHG abatement cost and primary resource demand. This was done using a bottom‐up mathematical optimization model, including the energy sectors and the chemicals sector, with electricity and biobased options considered. Results show that net‐zero GHG emissions for the considered chemicals in 2050 are attainable at a marginal cost of 640–900 €/tCO2‐eq, even with 26%–36% of demand being satisfied by fossil production routes. This is possible because renewable organic chemicals can act as carbon sinks if, at their end of life, C is permanently stored via landfilling or passed on to the next value chain via recycling. Nonetheless, considering the cost implications, the practical deployment of renewable chemicals is a challenge. The considered renewable chemicals cost 1.3–8 times more than their fossil counterparts, resulting in a marginal CO2 price of 480 €/tCO2‐eq when all primary resources (energy crops, forest residues and renewable electricity) are considered, or 810 €/tCO2‐eq when the availability of arable land is restricted. In the transition to net‐zero emissions for the chemicals under study, a circular economy is important not only for reducing demand for primary resources as is typically the case but also reduces GHG abatement costs by 13%–24% through carbon capture and utilization effects.

Environmentally-friendly preparation of Sn(II)-BDC supported heteropolyacid as a stable and highly efficient catalyst for esterification reaction

Facilitating energy resource deficiency and environmental contamination, this work focuses on sustainable biodiesel production through the esterification reactions of oleic acid (OA) with methanol. To address the reaction, a novel heterogeneous acid catalyst, 12-tungstophosphoric acid (TPA) immobilized on Sn-based MOFs (Sn(II)-BDC) was synthesized via a simple, green solvent, and easy-to-implement synthesis strategy for the first time, and applied effectively for esterification process of OA to produce biodiesel. The structure and composition of as-obtained catalyst have been verified using XRD, FTIR, N2 physisorption, SEM, EDX, TG, Py-FTIR, TPD-NH3, and XPS techniques. The obtained TPA/Sn(II)-BDC catalyst was found to be the best with 60 wt% of TPA loading, which resulted in an OA conversion of 91.7 % at optimized conditions of 0.15 g catalyst loading and methanol to OA molar ratio of 20:1 at temperature of 120 °C in 4 h, and the excellent performance arises from available pores structure, large amounts of acidic sites, good stability and the synergistic catalytic effect of TPA and Sn(II)-BDC. Furthermore, the composite catalyst reusability has been studied for five cycles, and it exhibits an acceptable conversion. This research provides a green and large-scale synthesis route for the sustainable production of biofuels by constructing heteropolyacids/Sn-based MOFs synergistic catalysts.