Equilibrium Conversion Research Articles

In situ exsolution of Ni–Co alloys from A-site-deficient perovskite for efficient ammonia decomposition

Developing efficient and robust catalysts for hydrogen production by ammonia decomposition is of importance towards the “zero-carbon” economy. Herein, a series of B-site Ni- and Co-doped A-site-deficient SrTiO3 perovskite (Sr0.9Ti0.8Ni0.1Co0.1O3-δ, STNC) with the in situ exsolution of NiCo nano-alloys were fabricated under reducing atmosphere. The Ni–Co/STO (SrTiO3) catalyst derived from STNC shows much higher activity for ammonia decomposition than those Ni and Ni–Co based catalysts fabricated by impregnation. The STNC derived sample can produce 32.6 mmol gcat−1·min−1 hydrogen at 600 °C, 2.2 and 1.9 fold higher than those of Ni/STO and Ni–Co/STO. Furthermore, the synthesis methods including the Pechini, hydrothermal and ball milling methods were investigated for the preparation of the exsoluted Ni–Co catalysts toward ammonia decomposition. The STNC–HT catalyst by hydrothermaldemonstrated an excellent performance and reached 70% and a near equilibrium conversion of ammonia under 600 and 650 °C with a WHSV of 30,000 mL gcat−1h−1. The relationship between structure and performance was further studied by a series of characterizations. In addition, the STNC–HT catalyst was employed in the direct ammonia solid oxide fuel cells, in which the performance is closely related to the ammonia decomposition activity, and shows a satisfying power density of 99.3 mW cm−2. Generally, we identified an approach to engineer catalysts with enhanced activity for the ammonia utilization as energy vectors in our work.

Electrochemical Ammonia Synthesis at Intermediate Temperatures Using Solid-State Phosphate Electrolyte

As we aim to realize a carbon-neutral sustainable society and a CO2-free society, methods of converting renewable energy into hydrogen and then further into a hydrogen carrier with high energy density are attracting much attention. Among various energy carrier materials, ammonia is regarded as a promising candidate, which has a high hydrogen content and is easy to transport and store. Currently, ammonia is industrially produced by the Haber-Bosch process under high-temperature and high-pressure conditions, which is energy intensive and has a large environmental impact. Therefore, in this study, we focused on electrolytic synthesis under mild conditions.Due to the operating temperature constraints of the electrolyte, ammonia electrosynthesis is mainly classified into three temperature ranges: low temperature range below 100℃, high temperature range above 500℃, and medium temperature range from 100℃ to 500℃. Since ammonia synthesis from hydrogen and nitrogen is exothermic, synthesis at a low temperature is thermodynamically advantageous, but the disadvantage is that the reaction rate is limited because N2 molecules are difficult to active at low temperatures. On the other hand, although NH3 synthesis proceeds at a high reaction rate in the high temperature range, decomposition of ammonia in the reverse reaction is also likely to occur, leading to low equilibrium conversion of N2. Based on these considerations, we target NH3 synthesis in the intermediate temperature range, which is expected to have both the advantages of the low-temperature and high-temperature types, namely thermodynamic and kinetic advantages. In addition, ammonia synthesis was performed using a solid-state phosphate electrolyte that exhibits high proton conductivity and stability in the intermediate temperature range, and research focus was posed on cathode catalysts to raise the ammonia production rate and faradaic efficiency simultaneously. In this study, we have investigated Fe, which has a high dissociation activity for nitrogen molecules, and the first candidate for the cathode catalyst was a composite catalyst of Fe and yttrium-doped barium zirconate (BZY), that had shown the yield rate and faradaic efficiency at 220℃ and ambient pressure. [1]First, ammonia electrosynthesis was performed using Fe/BZY-Ru as cathode catalyst, in which RuO2 was added to Fe/BZY to maintain the reduced state of Fe. The highest NH3 yield rate of 2.7x10-10 mol (s cm2)-1 was achieved at -1.5 V (vs. open-circuit voltage (OCV)) and the highest faradaic efficiency of 0.3% was achieved at -0.5 V (vs. OCV). This low faradaic efficiency was thought to be derived from H2 generation as a side reaction of NH3 generation, so we started electrosynthesis using Fe/BZY without RuO2 as a cathode catalyst. As a result, the faradaic efficiency of 4.8％ was achieved at -1.5 V (vs. OCV) with the NH3 yield rate of 2.1x10-10 mol (s cm2)-1.[1] Y. Yuan, S. Tada, R. Kikuchi, Mater. Adv., 2, 793 (2021).

Phase Effects in Zirconia Catalysed Glucose Conversion to 5-(Hydroxymethyl)furfural.

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-ZrO2 with 85 wt % t-ZrO2 in either batch or packed bed reactor configuration is sufficient to reach equilibrium conversion of glucose for subsequent dehydration by the t-ZrO2 component. Under continuous flow, a six-fold increase in HMF production was obtained when operating with a physical mixture of m- and t-ZrO2 compared to that from a single bed of t-ZrO2.

2-O-α-D-glucosyl glycerol production by whole-cell biocatalyst of lactobacilli encapsulating sucrose phosphorylase with improved glycerol affinity and conversion rate

Background2-O-α-D-glucosyl glycerol (2-αGG) is a valuable ingredient in cosmetics, health-care and food fields. Sucrose phosphorylase (SPase) is a favorable choice for biosynthesis of 2-αGG, while its glucosyl-acceptor affinity and thermodynamic feature remain largely unknown, limiting 2-αGG manufacturing.ResultsHere, three SPases were obtained from lactobacilli and bifidobacteria, and the one encoded by Lb. reuteri SDMCC050455 (LrSP) had the best transglucosylation ability, with 2-αGG accounting for 86.01% in the total product. However, the LrSP exhibited an initial forward reaction rate of 11.83/s and reached equilibrium of 56.90% at 110 h, indicating low glycerol affinity and conversion rate. To improve catalytic efficiency, the LrSP was overexpressed in Lb. paracasei BL-SP, of which the intracellular SPase activity increased by 6.67-fold compared with Lb. reuteri SDMCC050455. After chemically permeabilized with Triton X-100, the whole-cell biocatalysis of Lb. paracasei BL-SP was prepared and showed the highest activity, with the initial forward reaction rate improved to 50.17/s and conversion rate risen to 80.79% within 17 h. Using the whole-cell biocatalyst, the final yield of 2-αGG was 203.21 g/L from 1 M sucrose and 1 M glycerol.ConclusionThe food grade strain Lb. paracasei was used for the first time as cell factory to recombinantly express the LrSP and construct a whole-cell biocatalyst for the production of 2-αGG. After condition optimization and cell permeabilization, the whole-cell biocatalyst exhibited 23.89% higher equilibrium conversion and 9.10-fold of productivity compared with the pure enzyme catalytic system. This work would provide a reference for large-scale bioprocess of 2-αGG.

Membrane reformer technology for sustainable hydrogen production from hydrocarbon feedstocks

Hydrogen (H2) is receiving growing interest as a clean energy carrier as the world’s energy system transitions towards net zero. Today, H2 is primarily produced from hydrocarbons using the steam methane reforming (SMR) process. This well-established method converts methane-rich gas into syngas, which is further treated with steam to increase H2 yield via the water-gas-shift (WGS) process. However, this conventional route results in high carbon intensity of 10 tons CO2/ton of H2. Therefore, there is a growing need for sustainable H2 production technologies that utilize existing fossil energy sources and infrastructure while minimizing carbon emissions and costs.Membrane reactors (MR) are a promising technology for sustainable H2 production from hydrocarbons. A H2-selective palladium-alloy (Pd–Au) membrane is integrated within the catalyst bed, creating a system where H2 production and separation occur simultaneously in a single unit. This integration offers several advantages over the conventional system; process intensification allows thermodynamic equilibrium conversion limitations to be overcome while producing high purity (>99%) H2 at milder operating temperatures of ∼550 °C compared to 800–1000 °C in conventional packed bed reactors. Downstream processes such as WGS reactors and pressure swing adsorption are eliminated, resulting in reduced capital and operating costs. Moreover, the by-product stream remains pressurized at 25–40 bar and contains CO2 at concentrations above 60%, enabling CO2 capture at reduced cost.

Ultrasound-assisted synthesis of methyl acrylate using Amberlyst-15 catalyst: Optimization using response surface method

Ultrasound-assisted synthesis of methyl acrylate was performed in a solvent-free ultrasound batch reactor using acid ion exchange resin (amberlyst-15) as a heterogeneous catalyst. Influence of different reaction parameters such as temperature (40–70°C), alcohol to acid mole ratio (2–8), catalyst loading (0–10 % w/w), and addition of molecular sieves (0–8 %), ultrasound power (0–120 W), and duty cycle (20–80 %) on the activity of reaction were investigated through one parameter at a time. Further, four significant parameters were optimized using response surface methodology using a central composite design. The maximum conversion of acrylic acid 61.02 %, was obtained at optimum reaction conditions at 61°C reaction temperature, 6.5 alcohol to acid mole ratio, 7.85 % catalyst loading, and 60 % ultrasound duty cycle. The equilibrium conversion improved from 29.2 % to 61.02 %, with a significant decrease in reaction time as compared to the conventional approach.

A thermodynamic consideration on the synthesis of methane from CO, CO2, and their mixture by hydrogenation

The synthesis of methane from CO and CO2 by hydrogenation is now considered as a promising route in effectively storing hydrogen energy as well as sustainably producing fuels and chemicals, while many reaction details involved in such processes, in particular for the hydrogenation of the CO and CO2 mixture, are not yet adequately understood. As a supplement to our previous works on the hydrogenation of CO and CO2 into alcohols and hydrocarbons, a thermodynamic consideration is made in this work to evaluate the potential and limit for the synthesis of methane from CO, CO2, and their mixture in particular. The results consolidate that in comparison with single CO or CO2, their mixture is probably more credible in practice for the production of methane by hydrogenation, where the overall C-based methane yield can be used as the major index to evaluate the process efficiency. The hydrogenation of CO shows a higher equilibrium yield of methane than the hydrogenation of CO2, while the overall C-based equilibrium yield of methane for the hydrogenation of the CO and CO2 mixture just lies in between and decreases almost lineally with the increase of the CO2/(CO+CO2) molar ratio in the feed, despite the great change in the equilibrium conversions of CO and CO2 with the feed composition. Nevertheless, an adequate overall C-based equilibrium yield of methane (> 85%) can be achieved at a temperature lower than 400 °C and a pressure higher than 0.1 MPa for the stoichiometric hydrogenation of CO, CO2, or their mixture whichever. These results should be beneficial to the design of more efficient catalysts and processes for the hydrogenation of CO/CO2 to methane.

Highly effective direct conversion of H2S into COx-free H2 and S at low temperature over novel MoxC@ZrO2 microwave catalysts

Direct decomposition of H2S into H2 and S is an attractive alternative to the Claus process, because COx-free H2 and S can be simultaneously recovered from an abundant and toxic waste gas, which has huge social economic and ecological environmental benefits. However, it is still a great challenge to achieve the direct H2S decomposition reaction with high efficiency due to the thermal equilibrium limitation. Herein, a core-shell structured MoxC@ZrO2 was developed as novel microwave catalyst for microwave catalytic H2S decomposition. More specifically, the H2S conversion over MoxC@ZrO2 catalyst is as high as 99.9% at 650 °C, which immensely surpasses the H2S equilibrium conversion (6.1% at 650 °C). This study provides an effective strategy for the design of highly active microwave catalysts, and supplies a strategy for efficiently catalytic decomposition of H2S waste and recovering high-value hydrogen and sulfur at lower reaction temperatures.

Propylene carbonate synthesis routes using CO2: DFT and thermodynamic analysis

Propylene carbonate (PC) is utilized to improve performance and stability in lithium-ion batteries as an electrolyte component and as a high-performance solvent in paints, varnishes, and adhesives. It is a versatile chemical used in many different industries. It also functions as a plasticizer in polymers and a solvent in pharmaceutical and cosmetic formulations. In the current work, chemical equilibrium analyses of a number of potential processes involved in the synthesis of PC were conducted. To examine the thermodynamic viability of all five approaches, the fluctuation of ΔGmo with temperature for the key processes of PC synthesis was investigated in a specific temperature range of 25 °C-180 °C and at 1 bar and 60 bar pressures. The heat capacity values were estimated using the Rozicka-Domalski method. Benson Group-Increment Theory (BGIT) was used to evaluate the unknown ΔfH for a molecule. By examining the impact of temperature (25 °C-180 °C) and pressure (0–100 bars) on chemical equilibrium constant and equilibrium conversion of reactants, the main reactions of PC synthesis pathways were compared. It was discovered that the one-pot synthesis route and the o-chloropropanol and CO2 approach were superior. The DFT calculations were performed to study the energy changes taking place to convert propylene, glycerol, and propylene glycol (PG) into PC. Both thermodynamic and DFT calculations proved that the PG and urea route is the least favorable for synthesizing PC.

Modeling & experimental studies on enhancement of H2S conversion using catalytic membrane reactor for hydrogen production

Abstract Acidic gases such as H2S and CO2 are generated in the refineries during coal gasification. These pollutant gases need to be treated before releasing to the atmosphere. Conventionally, H2S gas is treated by Claus process in which H2S is converted to elemental S and H2O, in presence of O2 at ∼1,200 K. In the present energy scenarios, hydrogen has got importance as a source of clean fuel for industrial application. The H2S generated in the refineries can be a potential precursor of hydrogen. If this hydrogen can be obtained by thermal decomposition of H2S, that can increase the overall economic value of the H2S containing streams and the produced hydrogen can be used for hydrocracking and hydro-treating in refineries, as well as to synthesize value-added products for chemical industries. However, H2S thermal decomposition is an endothermic and equilibrium limited reaction (equilibrium conversion is only ∼15 % at 1,000 K), requiring a very high temperature (∼1,500 K) to achieve even a conversion of greater than 40 %. Packed Bed Catalytic Membrane Reactor (PBCMR) for thermal decomposition of H2S can be a potential technology augmentation and process intensification to increase this equilibrium conversion. In this work, modeling and experimental studies of H2S thermal decomposition using in-house designed & developed PBCMR have been carried out. The modeling studies were validated with experimental data. Clay-alumina ceramic tubular membrane (L: 250 mm; OD: 12 mm; thickness: 2 mm) was fabricated using extrusion process having an average membrane pore size of ∼1 μm and with a porosity of ∼20 %. Pt (2 %) coated alumina extrudes were used as catalyst to accelerate the reaction kinetics. Experimental studies showed that H2S to hydrogen conversion of ∼90 % is achieved using PBCMR at ∼1,523 K, compared to only ∼40 % conversion in a conventional packed bed tubular reactor (without membrane). Modelling studies were carried out to study the influence of operating parameters such as, reactor wall temperature, feed temperature, pressure and feed velocity. Studies showed that reactor wall temperature is having the most dominant effect on H2S conversion, which is confirmed by experimental findings. The studies offer useful insights into the application of PBCMR technology for management of waste gas stream containing H2S and recovery of hydrogen.

Direct Non-Oxidative Methane Conversion and Hydrogen Co-Production in a Proton Conducting Membrane Reactor

Direct Non-oxidation Methane Conversion (DMNC) has been recognized a promising technology for the upgrading of cheap and abundant methane to higher hydrocarbons (C2+) and H2, but this technology has not been commercialized yet because of the low methane equilibrium conversion and severe carbon deposition.1-3 Here, we present our effort to develop a proton conducting membrane reactor (SrCe0.7Zr0.2Eu0.1O3- ⴃ) combined with the catalysts (Fe©SiO2) to circumvent the equilibrium limitations of the DMNC reaction and solve the coking (i.e., solid carbon deposition) problem. By coupling the Fe©SiO2 catalysts with H2 permeable membrane reactor, part of produced H2 during the catalytic conversion can be extracted from the effluent gas, which not only provides a one-step hydrogen production without additional separation process, but also shifts the equilibrium of the reaction to the product side and achieves an improved methane conversion and higher C2+ yield when compared to the traditional fixed-bed reactor. In addition, an air sweep outside the reactor results in O-permeation into catalyst to oxidize any deposited carbon to CO thus preventing coking.The membranes were fabricated using tape casting of the support layer followed by dip coating process to form the dense membrane layer. Using this method, we obtained 25 µm for the thickness of the dense layer and around 700 µm for the thickness of the support layer (see Fig. 1a and 1b). The catalyst was synthesized by a simple sol-gel method followed by fusing process, and then was crushed into 40-80 mesh and loaded inside of membrane reactor to test.The performance metrics include methane conversion, selectivity, and product yield. Our membrane reactor achieved single-pass methane conversion of 17.5%, and a C2+ yield of 15% (see Fig. 1c) at 1323K.Finally, our membrane reactors were stable for over 350 hours, which, along with the aforementioned performance metrics, constitutes a major advance in the development of commercial DMNC technology. References Guo, X.; Fang, G.; Li, G.; Ma, H.; Fan, H.; Yu, L.; Ma, C.; Wu, X.; Deng, D.; Wei, M.; Tan, D.; Si, R.; Zhang, S.; Li, J.; Sun, L.; Tang, Z.; Pan, X.; Bao, X., Direct Nonoxidative Conversion of Methane to Ethylene, Aromatics, and Hydrogen. Science 2014, 344 (6184), 616-619.Thyssen, V. V.; Vilela, V. B.; de Florio, D. Z.; Ferlauto, A. S.; Fonseca, F. C., Direct Conversion of Methane to C2 Hydrocarbons in Solid-State Membrane Reactors at High Temperatures. Chemical Reviews 2022, 122 (3), 3966-3995.Sakbodin, M.; Schulman, E.; Cheng, S.; Huang, Y.-L.; Pan, Y.; Albertus, P.; Wachsman, E. D.; Liu, D., Direct Nonoxidative Methane Conversion in an Autothermal Hydrogen-Permeable Membrane Reactor. Advanced Energy Materials 2021, 11 (46), 2102782. Figure 1

Close Intimacy between PtIn Clusters and Zeolite Channels for Ultrastability toward Propane Dehydrogenation.

Propane dehydrogenation (PDH) serves as a pivotal intentional technique to produce propylene. The stability of PDH catalysts is generally restricted by the readsorption of propylene which can subsequently undergo side reactions for coke formation. Herein, we demonstrate an ultrastable PDH catalyst by encapsulating PtIn clusters within silicalite-1 which serves as an efficient promoter for olefin desorption. The mean lifetime of PtIn@S-1 (S-1, silicalite-1) was calculated as 37317 h with high propylene selectivity of >97% at 580 °C with a weight hourly space velocity (WHSV) of 4.7 h-1. With an ultrahigh WHSV of 1128 h-1, which pushed the catalyst away from the equilibrium conversion to 13.3%, PtIn@S-1 substantially outperformed other reported PDH catalysts in terms of mean lifetime (32058 h), reaction rates (3.42 molpropylene gcat-1 h-1 and 341.90 molpropylene gPt-1 h-1), and total turnover number (14387.30 kgpropylene gcat-1). The developed catalyst is likely to lead the way to scalable PDH applications.

Pt3Mn/SiO2 + ZSM-5 Bifunctional Catalyst for Ethane Dehydroaromatization

Ethane dehydroaromatization (EDA) is a potentially attractive process for converting ethane to valuable aromatics such as benzene, toluene, and xylene (BTX). In this study, a Pt3Mn/SiO2 + ZSM-5 bifunctional catalyst was used to investigate the effect of dehydrogenation and the Brønsted acid catalyst ratio, hydrogen partial pressure, and reaction temperature on the product distributions for EDA. Pt3Mn/SiO2 + ZSM-5 with a 1/1 weight ratio showed the highest ethane conversion rate and BTX formation rate. Ethylene is initially formed by dehydrogenation by the Pt3Mn catalyst, which undergoes secondary reactions on ZSM-5, forming C3+ reaction intermediates. The latter form final products of CH4 and BTX. At conversions from 15 to 30%, the BTX selectivities are 82–90%. For all bifunctional catalysts, the ethane conversion significantly exceeds the ethane–ethylene equilibrium conversion due to reaction to secondary products. Low H2 partial pressures did not significantly alter the product selectivity or conversion. However, higher H2 partial pressures resulted in increased methane and decreased BTX selectivity. The excess hydrogen saturated the olefin intermediates to form alkanes, which produced methane by monomolecular cracking on ZSM-5. With an increasing reaction temperature from 550 °C to 650 °C, the benzene selectivity increased, while the highest BTX selectivity was obtained at 600 to 650 °C.

Waste CO2 capture and utilization for methanol production via a novel membrane contactor reactor process: Techno-economic analysis (TEA), and comparison with other existing and emerging technologies

We introduced recently a CO2 capture and utilization (CCU) technology that produces methanol (MeOH), from waste CO2 employing a novel configuration combining a reverse water gas shift reactor (RWGSR) with a membrane contactor reactor for MeOH synthesis (MeS-MCR). The integrated RWGSR/MeS-MCR process overcomes the challenges direct CO2 conversion into MeOH faces and achieves carbon conversions exceeding 80 %, significantly surpassing the equilibrium conversion of ∼ 20–30 % for the MeS reaction. In this study, a techno-economic analysis (TEA) was conducted on the RWGSR/MeS-MCR process along with four other CO2-to-MeOH CCU processes. Key economic parameters, as well as the energy efficiency, were analyzed with respect to CO2 and renewable hydrogen (H2) costs and plant capacity. The study revealed that the RWGSR/MeS-MCR technology has the highest energy efficiency and the best economic performance among all the technologies investigated. All technologies offer the significant societal benefit of capturing and utilizing waste CO2, but under present CO2 and renewable H2 costs, they cannot currently compete cost-wise with conventional MeOH production methods. However, under a future scenario whereby government incentives lower the CO2 cost and technological advances decrease the price of renewable H2, the proposed RWGSR/MeS-MCR process and another catalytic technology (CAMERE) become price competitive.

An active, stable cubic molybdenum carbide catalyst for the high-temperature reverse water-gas shift reaction.

Although technologically promising, the reduction of carbon dioxide (CO2) to produce carbon monoxide (CO) remains economically challenging owing to the lack of an inexpensive, active, highly selective, and stable catalyst. We show that nanocrystalline cubic molybdenum carbide (α-Mo2C), prepared through a facile and scalable route, offers 100% selectivity for CO2 reduction to CO while maintaining its initial equilibrium conversion at high space velocity after more than 500 hours of exposure to harsh reaction conditions at 600°C. The combination of operando and postreaction characterization of the catalyst revealed that its high activity, selectivity, and stability are attributable to crystallographic phase purity, weak CO-Mo2C interactions, and interstitial oxygen atoms, respectively. Mechanistic studies and density functional theory (DFT) calculations provided evidence that the reaction proceeds through an H2-aided redox mechanism.

Enhancing the stability of a novel D-allulose 3-epimerase from Ruminococcus sp. CAG55 by interface interaction engineering and terminally attached a self-assembling peptide

D-allulose, a highly desirable sugar substitute, is primarily produced using the D-allulose 3-epimerase (DAE). However, the availability of usable DAE enzymes is limited. In this study, we discovered and engineered a novel DAE Rum55, derived from a human gut bacterium Ruminococcus sp. CAG55. The activity of Rum55 was strictly dependent on the presence of Co2+, and it exhibited an equilibrium conversion rate of 30.6 % and a half-life of 4.5 h at 50 °C. To enhance its performance, we engineered the interface interaction of Rum55 to stabilize its tetramer structure, and the best variant E268R was then attached with a self-assembling peptide to form active enzyme aggregates as carrier-free immobilization. The half-life of the best variant E268R-EKL16 at 50 °C was dramatically increased 30-fold to 135.3 h, and it maintained 90 % of its activity after 13 consecutive reaction cycles. Additionally, we identified that metal ions played a key role in stabilizing the tetramer structure of Rum55, and the dependence on metal ions for E268R-EKL16 was significantly reduced. This study provides a useful route for improving the thermostability of DAEs, opening up new possibilities for the industrial production of D-allulose.

Novel synthesis of CuFe2O4/g-C3N4 based on microwave ferromagnetic resonance effect for the thorough removal of TC in mariculture wastewater under natural sunlight

Superior separation of photogenerated carriers holds the key to intensive degradation of tetracycline (TC) in mariculture wastewater under natural sunlight. CuFe2O4/g-C3N4 (CFO/g) was synthesized by secondary microwave co-precipitation (SMCP) based on the ferromagnetic resonance absorption effect. Under the reaction conditions of pH = 6.5, CFO/g = 0.2 g/L, [H2O2] = 1 mM, 99.0 % TC removal was realized in 40 min. Enhanced performance for TC removal in high-salinity environments heavily relied on elevated ionic strength and rapid electron transfer of CFO/g in conjunction with high-salinity interactions. To ecologically remediate mariculture wastewater under natural sunlight, we immobilized powdered CFO/g to a ferrite magnet and devised a continuous flow reaction apparatus, incorporating the controlled injection of hydrogen peroxide (H2O2), to achieve the 100 % TC removal and simultaneously undertake the pretreatment of other contaminants (∼70 %). Ultimately, a safety assessment demonstrated that the degradation of mariculture wastewater by the CFO/g photo-Fenton system is a reliable and efficient technology, and the growth of clownfish remained unimpaired. SMCP successfully accelerated the conversion of high-valent metal ions to low-valent ones and eased the activation barriers of H2O2, enabling various active species to execute their respective roles productively. Innovative application of microwave resonance to enhance the magnetic properties of CFO/g and to support the equilibrium conversion of elemental valence states in high-salinity environments from real wastewater.

Revisiting the Potential of Group VI Inorganic Precatalysts for the Ethenolysis of Fatty Acids through a Mechanochemical Approach.

The utilization of biobased feedstocks to prepare useful compounds is a pivotal trend in current chemical research. Among a varied portfolio of naturally available starting materials, fatty acids are abundant, versatile substrates with multiple applications. In this context, the ethenolysis of unsaturated fatty acid esters such as methyl oleate is an atom-economical way to prepare functional C10 olefins with a biobased footprint. Despite the existence of a variety of metathesis catalysts for the latter process, there is a lack of readily available, efficient, and inexpensive catalytic systems based on earth-abundant metals (Mo, W) whose preparation does not require sophisticated syntheses and manipulations. Here, a systematic exploration of homogeneous and heterogeneous inorganic Mo, W (oxy)halides shows that MoOCl4, while inactive as a homogeneous species, forms active and selective silica-supported ethenolysis precatalysts able to reach equilibrium conversion of methyl oleate within a few minutes upon activation with SnMe4. Such heterogeneous MoOCl4-based precatalysts were easily accessed through mechanochemical solvent-free procedures and found to contain, upon characterization by elemental analysis and Raman spectroscopy, isolated (≡SiO)Mo(=O)Cl3 units or polymeric silica-supported [-O(≡SiO)nMoCl4-nO-]m (n = 1, 2) complexes depending on the molybdenum loading. The former isolated species exhibited a higher catalytic performance. The developed heterogeneous precatalysts could be applied to the ethenolysis of various substrates, including polyunsaturated fatty acid esters and industrial fatty acid methyl ester (FAME) mixtures from palm oil transesterification.

Selectivity control between reverse water-gas shift and fischer-tropsch synthesis in carbon-supported iron-based catalysts for CO2 hydrogenation

CO2 hydrogenation to chemicals and fuels has the potential to alleviate CO2 emissions and displace fossil resources simultaneously via consecutive RWGS and FTS reactions, also known as CO2-FTS. As Fe-based catalysts are active and selective for both reactions, their bifunctionality requires a delicate balance between the RWGS and FTS. In this work, we investigated the thermodynamic constraints of RWGS and CO2-FTS, the influence of CO2 conversion on selectivity and the influence of Fe nanoparticle size within the range of 4.7 to 10.3 nm. An inert carbon support was selected to rule out metal-support interaction and promoting effects of the support. Catalytic performance was evaluated at 300 °C, 11 bar, H2/CO2/Ar = 3/1/1, 600 to 72000 mL·gcat-1·h-1. At a CO2 conversion level below RWGS equilibrium conversion of 23 %, RWGS was found to be the primary and dominant reaction. No primary Sabatier reaction was observed. At higher CO2 conversion till the CO2-FTS threshold of 42 %, the secondary FTS reaction became dominant. Notably, a non-linear relation between CO2 conversion and CO selectivity was discovered. Comparing two catalysts with identical 5 wt% Fe loading but different average Fe nanoparticle size (6.6 and 8.4 nm), the 8.4 nm Fe catalyst was at least two times more active than the 6.6 nm Fe catalyst. In situ Mössbauer spectroscopy suggested a positive correlation between particle size, carburization and selectivity towards long-chain hydrocarbons. For these potassium-promoted carbon-supported Fe-based catalysts, nanoparticles of at least 8 nm are required for the formation of Fe carbides and improved reactivity.

Overcoming limitations in propane dehydrogenation by codesigning catalyst-membrane systems.

Propylene production through propane dehydrogenation (PDH) is endothermic, and high temperatures required to achieve acceptable propane conversions lead to low selectivity and severe carbon-induced deactivation of conventional catalysts. We developed a catalyst-membrane system that removes the hydrogen by-product and can thus achieve propane conversions that exceed equilibrium limits. In this codesigned system, a silica/alumina (SiO2/Al2O3) hollow-fiber hydrogen membrane was packed with a selective platinum-tin (Pt1Sn1/SiO2) PDH catalyst on the tube side with hydrogen diffusing from the tube to the shell side. We demonstrate that the catalyst-membrane system can achieve propane conversions >140% of the nominal equilibrium conversion with a propylene selectivity >98% without deactivation of the system components. We also show that by introducing oxygen on the shell side of the catalyst-membrane system, we can couple the endothermic PDH reaction on the tube side with exothermic hydrogen oxidation on the shell side. This coupling results in higher rates of hydrogen transport, leading to further enhancements in the propane conversion as well as desired thermoneutral system operation.