Solid-Acid Catalyzed Continuous-Flow Aminolysis of Epoxides.

We report a solid-acid catalyzed aminolysis of epoxides under continuous-flow conditions. A titania-zirconia supported molybdenum oxide catalyst demonstrated exceptional substrate compatibility, enabling the synthesis of ß-amino alcohols in excellent yields with high catalyst durability. Characterization of the catalyst revealed the crucial role of the titania-zirconia ratio in optimizing its performance. Furthermore, this method was applied to the efficient, sequential-flow synthesis of a rivaroxaban intermediate (an oral anticoagulant and the first direct factor Xa inhibitor), combining a hydrogenation step with the aminolysis reaction without the need for intermediate isolation.

Sucrose-derived porous carbon catalyzed lignin depolymerization to obtain a product with application in type 2 diabetes mellitus.

As the most important phenolic biopolymer in nature, lignin shows promising application potentialities in various bioactivities in vivo and in vitro, mainly including antioxidant, anti-inflammatory, hypolipidemic, and antidiabetic control. In this work, several carbon-based solid acids were synthesized to catalyze the fragmentation of organosolv lignin (OL). The generated lignin fragments, with controllable molecular weight and functional groups, were further evaluated for their application in the prevention and treatment of type 2 diabetes mellitus (T2DM). The results suggested that the urea-doped catalyst (SUPC) showed a more excellent catalytic performance in producing diethyl ether insoluble lignin (DEIL) and diethyl ether soluble lignin (DESL). In addition, the lignin fragments have a good therapeutic effect on the cell model of T2DM. Compared with the insulin resistance model, DEIL obtained by catalytic depolymerization of OL with SUPC could improve the glucose consumption of insulin-resistant cells. Moreover, low-concentration samples (50 µg/mL) can promote glucose consumption (19.7 mM) more than the traditional drug rosiglitazone (17.5 mM). This work demonstrates the prospect of depolymerized lignin for the prevention and treatment of T2DM and provides a new application field for lignin degradation products.

A solid acid derived from fishbone catalyzes the hydrolysis of cellulose into nanocellulose.

The necessity to look into waste biomass resource regeneration has increased due to growing environmental and energy-related problems. This study successfully developed an innovative fishbone-derived carbon-based solid acid catalyst using the carbonation-sulfonation method, which was subsequently applied to catalyze the hydrolysis of cellulose to produce nanocellulose. The data analysis reveals that the sulfonation treatment affects the microstructure of the catalyst, resulting in a decline in its specific surface area (134.48 m2/g decreased to 9.66 m2/g). However, this treatment doesn't hinder the introduction of acidic functional groups. In particular, the solid acid catalyst derived from fishbone exhibited a total acid content of 3.76 mmol/g, with a concentration of -SO3H groups at 0.48 mmol/g. Furthermore, the solid acids originating from fishbones manifested remarkable thermal stability, exhibiting a mass loss of <15 % at temperatures up to 600 °C. Moreover, the catalyst displayed exceptional catalytic performance during the cellulose hydrolysis reaction, achieving an optimum nanocellulose yield of 45.7 % at an optimized reaction condition. An additional noteworthy feature is the solid acid catalyst's impressive recyclability, maintaining a nanocellulose yield of 44.87 % even after undergoing five consecutive usage cycles. This research outcome underscores an innovative approach to for the sustainable utilization of waste biomass resources.

Design of Mn-based nanozymes with multiple enzyme-like activities for identification/quantification of glyphosate and green transformation of organophosphorus.

A Mn-based nanozyme, Mn-uNF/Si, with excellent alkali phosphatase-like activity was designed by in-situ growth of ultrathin Mn-MOF on the surface of silicon spheres, and implemented as an effective solid Lewis-Brønsted acid catalyst for broad-spectrum dephosphorylation. H218O-mediated GC-MS studies confirmed the cleavage sites and the involvement of H2O in the new bonds. DRIFT NH3-IR and in-situ ATR-FTIR confirmed the coexistence of Lewis-Brønsted acid sites and the adjustment of adsorption configurations at the interfacial sites. In addition, a green transformation route of "turning waste into treasure" was proposed for the first time ("OPs→PO43-→P food additive") using edible C. reinhardtii as a transfer station. By alkali etching of Mn-uNF/Si, a nanozyme Mn-uNF with laccase-like activity was obtained. Intriguingly, glyphosate exhibits a laccase-like fingerprint-like response (+,-) of Mn-uNF, and a non-enzyme amplified sensor was thus designed, which shows a good linear relationship with Glyp in a wide range of 0.49-750 µM, with a low LOD of 0.61 µM, as well as high selectivity and anti-interference ability under the co-application of phosphate fertilizers and multiple pesticides. This work provides a controllable methodology for the design of bifunctional nanozymes, which sheds light on the highly efficient green transformation of OPs, and paves the way for the selective recognition and quantification of glyphosate. Mechanistically, we also provided deeper insights into the structure-activity relationship at the atomic scale.

Efficient synthesis of some [1,3]-oxazine derivatives in the presence of solid acid nano catalyst based on ferrierite and study on their activity against breast cancer through molecular docking calculation.

In this research, the magnetic solid acid nanocatalyst based on ferrierite has been prepared and used as catalyst for the green synthesis of some [1,3]-oxazine derivatives in water at room temperature. The synthesized compounds were obtained in high to excellent yields after short reaction times and the structure of synthesized products were investigated by spectroscopic methods such as: FT-IR, 1H NMR and 13C NMR. The prepared magnetic solid acid catalyst was characterized using XRD, FT-IR, FE-SEM, EDX, elemental mapping, TGA and VSM analysis methods. Magnetic catalyst has easy separation ability, which leads to better and easier recycling. The preparation and synthesis of [1,3]-oxazine derivatives were carried out at room temperature in the presence of M-FER/TEPA/SO3H. Easy workup, green solvent (water) and also short reaction times with high to excellent yield of products, are some of advantageous of presented method. Docking calculations on the structure of the synthesized compounds proved their medicinal properties against breast cancer cells.

One-Pot Effective Approach to 2,5-Diformylfuran From Carbohydrates Using MoS2-Decorated Carbonaceous Sugarcane Bagasse.

Exploring the transformation of carbohydrates into valuable chemicals offers a promising and eco-friendly method for utilizing renewable biomass resources. Developing a bi-functional, sustainable heterogeneous catalyst is of utmost importance to attain a high level of selectivity for the desired product, 2,5-diformylfuran (DFF), in this direct conversion process. In this study, we developed a highly effective catalytic system to convert diverse carbohydrates into DFF. Our approach involved utilizing a MoS2 catalyst supported by amorphous carbon derived from sulfonated sugarcane biomass. The MoS2@SBG-SO3H composite was successfully synthesized using a facile and highly efficient method. The transformation of fructose into DFF achieved a significant yield of 70 % for 5 h at 160 °C using a one-step and one-pot reaction through dehydration and oxidation with oxygen. The oxidation of 5-hydroxymethylfurfural (HMF) into DFF using MoS2@SBG-SO3H was obtained at 94 % DFF within 5 h; the activation energy was 38.3 kJ . mol-1. The catalyst displayed convenient recovery and reusability. The direct synthesis of DFF from various carbohydrates, such as sucrose, glucose, maltose, and lactose, resulted in favorable yields. Our research provides a quick, green, and efficient process for preparing carbon-based solid acid catalysts and DFF.

Microwave Effect in Hydrolysis of Levoglucosan with a Solid Acid Catalyst for Pyrolysis-Based Cellulose Saccharification.

Pyrolysis-based saccharification consisting of fast pyrolysis followed by hydrolysis of the resulting anhydrosugars such as levoglucosan is a promising method for converting cellulosic biomass into glucose that can be used for producing biofuels and biochemicals. In the present study, hydrolysis of levoglucosan was evaluated in water with a polystyrene sulfonic acid resin (a solid acid catalyst) by heating under microwave irradiation or in an oil bath at 95 °C-120 °C. When the equilibrium temperature of the solution was the same, the conversion rate of levoglucosan was greater under microwave irradiation than in an oil bath. Model experiments indicate that the sulfonyl groups of the solid acid catalyst were selectively heated by microwave irradiation. The temperature of the reaction solution in the vicinity of the catalyst was locally higher than the equilibrium temperature of the solution, which enabled hydrolysis to proceed efficiently.

Nanostructured Solid/Liquid Acid Catalysts for Glycerol Esterification: The Key to Convert Liability into Assets.

Owing to the growing concerns about the dwindling fossil fuel reserves, increasing energy demand, and climate emergency, it is imperative to develop and deploy sustainable energy technologies to ensure future energy supply and to transition to the net-zero world. In this context, there is great potential in the biorefinery concept for supplying drop in biofuels in the form of biodiesel. Biodiesel as a fuel can certainly bridge the gap where electrification or the use of hydrogen is not feasible, for instance, in heavy vehicles and in the farm and marine transportation sectors. However, the biodiesel industry also generates a large amount of crude glycerol as the by-product. Due to the presence of several impurities, crude glycerol may not be a suitable feedstock for all high-value products derived from glycerol, but it fits well with glycerol esterification for producing glycerol acetins, which have numerous applications. This review critically looks at the processes using nanostructured solid/liquid acid catalysts for glycerol esterification, including the economic viability of the scale-up. The homogeneous catalysts reviewed herein include mineral acids and Brønsted acidic ionic liquids, such as SO3H-functionalized and heteropoly acid based ionic liquids. The heterogeneous catalysts reviewed herein include solid acid catalysts such as metal oxides, ion-exchange resins, zeolites, and supported heteropoly acid-based catalysts. Furthermore, the techno-economic analysis studies have shown the process to be highly profitable, confirming the viability of glycerol esterification as a potential tool for economic value addition to the biorefinery industry.

The mechanism of solid acid-catalyzed bamboo sawdust liquefaction under polyol systems.

Solid acid catalysts are widely used in the field of biomass catalytic conversion owing to their advantages of low environmental pollution, easy separation and reusability. Nevertheless, there are relatively few studies on the mechanism of solid acid liquefaction for biomass. In this study, the effect of acid strength and acid amount of various solid acids on the liquefaction efficiency has been investigated using waste bamboo sawdust generated from the pulp and paper industry as the raw material. In addition, the physicochemical changes of cellulose, hemicellulose and lignin during the reaction process of bamboo sawdust have been studied, and the liquefaction mechanism of bamboo sawdust under the action of various solid acids has been concluded. As a result, the liquefaction efficiency of bamboo sawdust under the polyol system of PEG400/propanetriol is mainly related to the acid strength of the solid acid, and the greater the acid strength of the solid acid, the better the catalytic effect on the bamboo sawdust, in which the residual amount of bamboo sawdust liquefaction catalyzed by the SPA catalyst is only 17.72%. Noteworthy, the most difficult component to liquefy is the crystallization of natural cellulose I into cellulose II during the reaction process, which is the primary obstacle to the complete liquefaction of bamboo sawdust by solid acid. Overall, these findings are valuable for the high value utilization of waste bamboo sawdust in the pulp and paper industry, as well as the application of solid acid catalytic technology for biomass.

Investigation into the Structure and Properties of Biochar Co-Activated by ZnCl2 and NaHCO3 under Low Temperature Conditions.

Using sodium lignosulfonate as feedstock, ZnCl2 and NaHCO3 co-activated the hierarchical porous carbons (HPCs) were prepared by one-pot pyrolysis with different NaHCO3 dosages (0-4 g) and carbonization temperatures (400-600 °C). Subsequently, phosphotungstate (HPW) was supported with the resulting biochar for the α-pinene hydration reaction to produce α-terpineol. The optimum preparation conditions were determined according to the yield of α-terpineol. The formation mechanism and physicochemical properties of HPCs were analyzed through TG, SEM, XPS, XRD, FT-IR, and N2 adsorption-desorption isotherms. The results demonstrated that NaHCO3 underwent a two-step reaction which liberated a substantial quantity of CO2, thereby enhancing activated carbon's macroporous and mesoporous structures. Simultaneously, NaHCO3 mitigated strong acid gas (HCl) emissions during ZnCl2 activation. Compared with AC450-4:8:0 prepared by ZnCl2 activation alone, the total pore volume of AC450-4:8:2 prepared by co-activation is increased from 0.595 mL/g to 0.754 mL/g and the mesopore rate from 47.7% to 77.8%, which is conducive to reducing the steric hindrance of the hydration reaction and improving the selectivity. Hydration experiments show that the selectivity of α-terpineol is 55.7% under HPW/AC450-4:8:2 catalysis, higher than 31.0% for HPW and 47.4% for HPW/AC450-4:8:0.

Synergistic Lewis and Brønsted Acid Sites Promote OH* Formation and Enhance Formate Selectivity: Towards High-efficiency Glycerol Valorization.

As a sustainable valorization route, electrochemical glycerol oxidation reaction (GOR) involves in formation of key OH* and selective adsorption/cleavage of C-C(O) intermediates with multi-step electron transfer, thus suffering from high potential and poor formate selectivity for most non-noble-metal-based electrocatalysts. So, it remains challenging to understand the structure-property relationship as well as construct synergistic sites to realize high-activity and high-selectivity GOR. Herein, we successfully achieve dual-high performance with low potentials and superior formate selectivity for GOR by forming synergistic Lewis and Brønsted acid sites in Ni-alloyed Co-based spinel. The optimized NiCo oxide solid-acid electrocatalyst exhibits low reaction potential (1.219 V@10 mA/cm2) and high formate selectivity (94.0 %) toward GOR. In situ electrochemical impedance spectroscopy and pH-dependence measurements show that the Lewis acid centers could accelerate OH* production, while the Brønsted acid centers are proved to facilitate high-selectivity formation of formate. Theoretical calculations reveal that NiCo alloyed oxide shows appropriate d-band center, thus balancing adsorption/desorption of C-O intermediates. This study provides new insights into rationally designing solid-acid electrocatalysts for biomass electro-upcycling.

A Stable Extra-Large Pore and High-Silica Zeolite Derived from Ge-Rich Precursor.

A multidimensional extra-large pore zeolite with highly hydrothermal stability, denoted as -IRT-HS, has been developed successfully, starting from Ge-rich germanosilicate precursor hydrothermally directed by a small and commercially available piperidinium-type organic structure-directing agent (OSDA). -IRT-HS, with the supermicropores, is structurally analogues to 28-membered ring -IRT topology as confirmed by various spectroscopic techniques. And it is the high-silica (Si/Ge=58) zeolite with the largest pore size as well. Notably, using acid-washed as-made Ge-rich -IRT precursor as the silicon source is crucial to restore partially collapsed structure into a stable framework by OSDA-assisted recrystallization. The calcined -IRT-HS maintains a high crystallinity, even when stored in a humid environment for extended periods or directly exposed to water. Additionally, high silica Al-containing analogue is also readily synthesized, serving as an active solid-acid catalyst in 1,3,5-triisopropylbenzene cracking reaction, yielding an impressive initial conversion up to 76.1 % much higher than conventional large-pore Beta zeolite (30.4 %). This work will pave the way for the designed synthesis of targeted high-silica zeolites with stable and extra-large pore frameworks, mimicking the structures of existing Ge-rich counterparts.

Acid-Base Cascades in Zeotype Single Crystal for Sugar Conversion.

The chemically catalyzed production of fructose syrup from high concentrations of glucose is crucial for the food industry and biorefining. In this work, a single crystal catalyst was synthesized via protective desilication of zeolite while incorporating indium. Glucose was isomerized in methanol at concentrations as high as 33 wt % before being hydrolyzed with water. The final fructose production was 54.9 %, with 89.1 % selectivity and 93.3 % sugar recovery, the highest isomerization rate at the highest concentration ever reported. Indium was present in the single-crystal catalyst as oxide nanoparticles and boundary framework atoms, and it achieved intelligent cooperation in the production of fructose syrup in methanol by catalyzing isomerization and selective glycosidation, minimizing degradation due to fructose accumulation and eliminating side reactions. This study contributed to the advancement of the industrial practice of chemically catalyzed glucose isomerization.

Insights into Preparation Methods and Functions of Carbon-Based Solid Acids.

With the growing emphasis on green chemistry and the ecological environment, researchers are increasingly paying attention to greening materials through the use of carbon-based solid acids. The diverse characteristics of carbon-based solid acids can be produced through different preparation conditions and modification methods. This paper presents a comprehensive summary of the current research progress on carbon-based solid acids, encompassing common carbonization methods, such as one-step, two-step, hydrothermal, and template methods. The composition of carbon source material may be the main factor affecting its carbonization method and carbonization temperature. Additionally, acidification types including sulfonating agent, phosphoric acid, heteropoly acid, and nitric acid are explored. Furthermore, the functions of carbon-based solid acids in esterification, hydrolysis, condensation, and alkylation are thoroughly analyzed. This study concludes by addressing the existing drawbacks and outlining potential future development prospects for carbon-based solid acids in the context of their important role in sustainable chemistry and environmental preservation.

Sulfonated P-W modified nitrogen-containing carbon-based solid acid catalysts for one-pot conversion of cellulose to ethyl levulinate under water-ethanol medium.

Converting cellulose (Cel) into ethyl levulinate (EL) is one of the promising strategies for supplying liquid fuels. In this paper, the prepared sulfonated P-W-modified N-containing carbon-based solid acid catalyst (PWNCS), in which the Polyaniline (PANI) was employed as N and C precursors, successfully converted Cel into EL under the water-ethanol medium. The characterization results demonstrated that a tiny addition of P increased the Brønsted acid sites (BAS) content and defective WO3 provided the Lewis acid sites (LAS), meanwhile, the sulfonation process did not change the fundamental structure but introduced the sulfonic groups to dramatically increase the acidic content. Therefore, under optimized reaction conditions, PWNCS realized about 100% Cel conversion and 71.61% of EL yield, furthermore, the selectivity of EL reached 89.14%. In addition, the effect of water on the reaction pathway of Cel to EL over PWNCS was proposed. The addition of water generally resulted in the hydration of defective WO3 to reduce the LAS and increase BAS, which significantly inhibited the side reactions of retro-aldol condensation (RAC) and subsequent etherification reactions during Cel conversion and then improved the selectivity of EL.

Unveiling the mechanisms of carboxylic acid esterification on acid zeolites for biomass-to-energy: A review of the catalytic process through experimental and computational studies.

In recent years, there has been significant interest from industrial and academic areas in the esterification of carboxylic acids catalyzed by acidic zeolites, as it represents a sustainable and economically viable approach to producing a wide range of high-value-added products. However, there is a lack of comprehensive reviews that address the intricate reaction mechanisms occurring at the catalyst interface at both the experimental and atomistic levels. Therefore, in this review, we provide an overview of the esterification reaction on acidic zeolites based on experimental and theoretical studies. The combination of infrared spectroscopy with atomistic calculations and experimental strategies using modulation excitation spectroscopy techniques combined with phase-sensitive detection is presented as an approach to detecting short-lived intermediates at the interface of zeolitic frameworks under realistic reaction conditions. To achieve this goal, this review has been divided into four sections: The first is a brief introduction highlighting the distinctive features of this review. The second addresses questions about the topology and activity of different zeolitic systems, since these properties are closely correlated in the esterification process. The third section deals with the mechanisms proposed in the literature. The fourth section presents advances in IR techniques and theoretical calculations that can be applied to gain new insights into reaction mechanisms. Finally, this review concludes with a subtle approach, highlighting the main aspects and perspectives of combining experimental and theoretical techniques to elucidate different reaction mechanisms in zeolitic systems.

Cellulose hydrolysis reactor incorporating stirring apparatus for use with carbon-based solid acid catalyst.

A highly efficient reactor with a stirring device was specially designed with the intent of performing the hydrolysis of pure crystalline cellulose using a carbon-based solid acid catalyst. This catalyst comprised an amorphous carbon-based material bearing -SO3H, -COOH and -OH groups. The stirring apparatus had seven blades coated with polytetrafluoroethylene and arranged axially at regular intervals with a 60° offset. This design proved highly effective, providing double the glucose yield compared with conventional stirring systems. The basic properties of this novel reactor were investigated and analyzed and are discussed herein.

Effect and mechanism of ultrasound on acid loading in the preparation of silicon-based sulfonic solid acids.

Silicon-based sulfonic solid acids have the advantages of high catalytic activity and selectivity, easy separation from products, low equipment corrosion, and environmental protection, and sulfuric acid loading is the key to their preparation. To overcome the shortcomings of low acid loading and uneven distribution in the existing preparation methods of micron-sized silicon-based sulfonic solid acids, a method was proposed to prepare micron-sized silicon-based sulfonic solid acids using ultrasonic enhanced technology. The effect of different reaction parameters, such as time, power, and temperature of ultrasonication, sulfonation temperature and time, and sulfuric acid concentration, on acid loading in solid acid was investigated in this work. The results showed that a micron-sized mesoporous silica-based solid acid was successfully synthesized with a high acid content of 0.8633 mmol/g, uniform acid distribution, high specific surface area of 269.332 m2/g, and large average particle size of 172.142 µm in this work. The introduction of ultrasound was found to expand the carrier's pore volume and increase the carrier's specific surface area and the number of hydroxyl groups, thereby increasing the acid loading capacity and the specific surface area of the solid acid sample by 66.6 % and 10.97 % respectively, compared with the case without ultrasound.

Powder properties of carbon-based solid acid catalyst for designing cellulose hydrolysis reactor with stirring apparatus.

The powder properties of a carbon-based solid acid catalyst, an amorphous carbon material bearing SO3H, COOH and OH groups, were investigated for the hydrolysis of cellulose. The Carr flowability and floodability indices, the angle of internal friction (adherence), and the particle size distribution and shape for the powder catalyst were determined. The need to develop a special reactor with a stirring apparatus for the hydrolysis of cellulose was determined based on the Carr flowability index. Insight into the interaction or adherence between the catalyst and crystalline cellulose during the hydrolysis process was gained by measuring the internal friction angle. The optimum moisture content in the catalyst to achieve the maximum adherence was investigated.

Preparation of Carbon-Based Solid Acid Catalyst from High-Sulfur Petroleum Coke with Nitric Acid and Ball Milling, and a Computational Evaluation of Inherent Sulfur Conversion Pathways.

A series of petroleum coke (petcoke)-derived solid acid catalysts were prepared via nitric acid treatment with or without ball milling pretreatment. The inherent sulfur in petcoke was converted to sulfonic groups, which were active sites for the esterification of octanoic acid and methanol at 60 °C, with ester yields of 14-43%. More specifically, samples without ball milling treated at 120 °C for 3 h had a total acidity of 4.67 mmol/g, which was 1.6 times that of the samples treated at 80 °C, despite their -SO3H acidities being similar (~0.08 mmol/g). The samples treated for 24 h had higher -SO3H (0.10 mmol/g) and total acidity (5.25 mmol/g) but not increased catalytic activity. Ball milling increased the defects and exposed aromatic hydrogen groups on petcoke, which facilitated further acid oxidation (0.12 mmol -SO3H/g for both materials and total acidity of 5.18 mmol/g and 5.01 mmol/g for BP-N-3/120 and BP-N-8/90, respectively) and an increased ester yield. DFT calculations were used to analyze the pathways of sulfonic acid group formation, and the reaction pathway with NO2• was the most thermodynamically and kinetically favourable. The activities of the prepared catalysts were related to the number of -SO3H acid sites, the total acidity, and the oxygen content, with the latter two factors having a negative impact.