High Recyclability Research Articles

Rational Integration of Nanozyme Probe and Smartphone Device for On‐Site Analysis

AbstractOn‐site detection featuring miniaturized, integrated analytical device and rapid data feedback has encouraged a great deal of attention, especially in the current context of pandemic diseases occurring with high frequency worldwide. This convenient detection device constitutes a stable recognition element and a portable signal treatment and readout module. In this regard, the enzyme‐mimic nanomaterials (nanozymes) with the merits of structural stability, cost efficiency, scale‐up synthesis and high recyclability well meet the requirements for recognition unit set‐up. While the all‐pervading smartphone, which enables the data collection through photography or wireless transmission, holds numerous opportunities in the design of hand‐held analytical device. In this review, we summarize the advances of nanozyme‐smartphone integrated platforms, with special emphasis of the signal transduction principles involving colorimetric, chemiluminescence, and electrochemical signals. The diversified on‐site applications in terms of biological, environment and food analysis are showcased. Finally, the current challenges as well as the future perspectives on nanozyme design, sensing diversity and smartphone analysis are discussed.

The recent development of β‐cyclodextrin‐based catalysts system in click reactions: A review

A significant challenge for scientists today is to design green and eco‐friendly catalysts based on green chemistry with high catalytic performance and recycling properties. Many studies have aimed to address environmental issues by developing green chemical processes and catalysts that reduce the production of harmful substances. β‐Cyclodextrin (β‐CD), a class of cyclic oligomers, has garnered considerable attention in recent decades. It has been utilized as a green alternative catalyst in various organic conversions, demonstrating satisfactory catalytic activity and improved efficiency of organic reactions. The availability, non‐toxicity, low cost, renewability, and high performance in organic transformations are several benefits of cyclodextrins that have attracted interest from research groups worldwide. The click reaction is well‐known in green chemistry for its high selectivity and efficiency in producing 1,2,3‐triazoles with significant medicinal activities. This reaction involves aryl/alkyl halides, alkynes, and NaN3 under ambient conditions to generate necessary scaffolds called 1,2,3‐triazoles. Therefore, finding green approaches for synthesizing 1,2,3‐triazoles is of great interest. In recent decades, significant advancements have been made in developing metal‐catalyzed click reactions to synthesize 1,2,3‐triazole derivatives. Carolyn Bertozzi, Morten Meldal, and Barry Sharpless were awarded the Nobel Prize in Chemistry in 2022 for their contributions to the foundations of click and bio‐orthogonal chemistry. In transition, metal‐catalyzed click reactions, using modified β‐CD derivatives as catalysts is particularly advantageous because of their valuable catalytic properties and their ability to form inclusion complexes with different metals. This review focuses on the catalyzed click reaction using β‐CD‐based catalysts to prepare triazoles. Using biodegradable β‐CD has made the method safe, sustainable, and eco‐friendly. The click reaction has provided access to various 1,2,3‐triazoles essential in pharmaceutical products and exhibits diverse biological activities. The specific purpose of this review is to summarize the application of β‐CD‐based catalyst systems in click reactions.

A Eu coordination polymer sensor for the detection of tartrazine, folic acid, and amino acids

In this work, 3-(2,4-dicarboxyphenyl)-6-carboxypyridine (H2ppda) and 4-(4-carboxyphenyl)benzoic acid (H2bpdc) were selected to synthesize a two-dimensional layered coordination polymer, [Eu(ppda)(bpdc)0.5(C2H5OH)(H2O)]n (Eu-1). Eu-1 is further hydrogen-bonded to construct a three-dimensional supramolecular structure. It has found that Eu-1 can be used as an excellent fluorescence sensor for the determination of food additives, such as tartrazine (TA), folic acid (FA), arginine (Arg), and lysine (Lys). Eu-1 showed high sensitivity, selectivity, recyclability, and anti-interference for the detection of TA, FA, Arg, and Lys in aqueous solution. The limits of detection TA, FA, Arg, and Lys are 9.87 × 10-8 M, 3.28 × 10−8 M, 2.20 × 10-6 M, and 9.46 × 10-7 M, respectively. Notably, it is the first example of luminescent coordination polymer to identify TA in aqueous system. In the meantime, a film utilizing Eu-1 as the key component had been successfully fabricated, and exhibited a remarkable potential for the visual recognition of TA and FA. In addition, the luminescence sensing mechanisms of Eu-1 on the above analytes were investigated further in detail.

All-in-one chitosan-based aerogel with a semi-clad structure for solar-driven interfacial evaporation

Solar-driven interfacial water evaporation is a promising technique for recovering clean fresh water and alleviating water scarcity. In this work, an all-in-one chitosan-based composite aerogel with a highly porous semi-clad structure was fabricated. In the process of interfacial water evaporation, the hydrophilic outer layer of the aerogel efficiently transported water to the upper surface through two-dimensional transport channels. Simultaneously, it rapidly converted absorbed sunlight into heat, demonstrating excellent photothermal conversion capabilities for efficient water evaporation. The hydrophobic inner core enabled the aerogel to float stably on the water surface, and had a low thermal conductivity to reduce heat dissipation into the water body. Under 1 sun illumination (1 kW m−2), the composite aerogel showed an evaporation rate of up to 1.547 kg m−2 h−1, corresponding to an evaporation efficiency of 91.47 %. Notably, the composite aerogel demonstrated high stability and recyclability in desalination and heavy metal wastewater treatment, which had great potential in recovering both clean water and heavy metal salts. The evaporator with a semi-clad structure had practical applications in solar desalination and sewage treatment due to its stable and efficient evaporation performance and simple preparation method.

Development of ligand-free Pd@TiO2 catalyst for efficient perfluoroalkylative carbonylation of terminal alkenes

The development of heterogeneous catalysts for the difunctionalization of olefins is of great scientific significance because of their sustainability in the manufacturing industry. Herein, we report a ligand free Pd@TiO2 catalyst that realized the perfluoroalkyl carbonylation of terminal olefins using carbon monoxide as the C1 source, providing sustainable access to β-perfluoroalkyl esters. This catalyst shows high activity, good recyclability, and broad functional group tolerance. The catalytic system developed here can reduce noble metal use and avoid using precious homogeneous phosphorus ligands, which are also toxic to the environment.

RSM approach for process optimization of the photodegradation of congo red by a novel NiCo2S4/chitosan photocatalyst

The current study reported a facile co-precipitation technique for synthesizing novel NiCo2S4/chitosan nanocomposite. The photocatalytic activity of the prepared nanocomposite was evaluated using congo red (CR) dye as a target pollutant. The central composite design was employed to examine the impact of different reaction conditions on CR dye degradation. This study selected the pH, photocatalyst loading, initial CR concentration and reaction time as reaction parameters, while the degradation efficiency (%) was selected as the response. A desirability factor of 1 suggested the adequacy of the model. Maximum degradation of 93.46% of 35 ppm dye solution was observed after 60 min of visible light irradiation. The response to surface methodology (RSM) is a helpful technique to predict the optimum reaction conditions of the photodegradation of CR dye. Moreover, NiCo2S4/Ch displayed high recyclability and reusability up to four consecutive cycles. The present study suggests that the prepared NiCo2S4/chitosan nanocomposite could prove to be a viable photocatalyst for the treatment of dye-contaminated wastewater.

Continuous fermentation using high cell density cell recycle system for L-lactic acid production.

For complete utilization of high glucose at ∼100 g/L, a high cell density (HCD) continuous fermentation system was established using Lb. delbrueckii NCIM 2025 for the bioproduction of lactic acid (LA). An integrated membrane cell recycling system coupled with the continuous bioreactor, aided to achieve the highest 34.77 g/L h LA productivity and 0.94-0.98 g/g yield. ∼34 times higher productivity was observed (in comparison to batch fermentation conducted in this study), when the continuous operations were carried out at the maximum dilution rate and wet cell weight i.e. 0.36 h-1 and 230 g/L, respectively. These results show the potential of this method for large-scale lactic acid production because it not only produces high titers but also ensures that glucose is used effectively. The method's superior performance in comparison to earlier studies suggests it as an affordable and sustainable alternative for the production of LA.

Phosphonate functionalized magnetic mesoporous silica for rare earth element recovery from citrate assisted solid waste extracts

The growing high demand of rare earth elements (REEs) has prompted extensive research on REE recovery from waste streams. This study reports the synthesis and evaluation of phosphonate-functionalized magnetic mesoporous silica (MMS-PP) for REE recovery from the acidic extracts of solid wastes. MMS-PP was synthesized using surfactant template and post-synthesis methods, and tested using simulated and real extraction solutions from citrate-assisted REE extracts from municipal solid waste incineration (MSWI) ash. The organic-inorganic hybrid MMS-PP was evaluated for La recovery from 50 mM simulated citrate extract, with the adsorption capacity of 13.5 mg/g compared to ∼2.5 mg/g for non-functionalized MMS. The MMS-PP material exhibited fast adsorption within 10 min, good La selectivity against competing Na+ and Ca2+, moderate selectivity against Al3+ and Fe3+, high recyclability over multiple adsorption-desorption cycles, and equivalent efficiency for La, Ce, Nd, and Y recovery. The MMS-PP material also demonstrated 70–95% REE recovery from real citrate extracts of MSWI ash, and the spent MMS-PP material can be regenerated and reused for multiple cycles. Functionalized mesoporous materials in combination with organic-ligand assisted extraction can potentially provide a green, effective, and tunable solid-liquid separation platform for REE recovery from complex solid waste streams.

Synthesis of Nitrogen- and Oxygen-Containing Heterocycles Catalysed by Metal Nanoparticles Reported in 2022

AbstractThe versatility of aza- and oxa-heterocyclic compounds has garnered significant attention in recent times. A large number of currently approved pharmaceutical products include nitrogen- and oxygen-containing heterocycles. Recent nanotechnological developments have propelled an upsurge in the applications of nanocatalysis for heterocyclic synthesis. Metal nanoparticles (MNPs) have emerged as promising catalysts for the synthesis of aza- and oxa-heterocycles owing to their unique physicochemical properties. Various MNPs including gold, silver, nickel and palladium have been evaluated for their catalytic activities in different reaction types, including cyclisation, coupling, hydrogenation and oxidative transformations. The MNPs have exhibited remarkable catalytic efficiency when utilised under optimal conditions. These catalysts have showcased high reusability and recyclability, yielding satisfactory amounts of the desired heterocyclic compound. The present work provides a detailed overview of recent advances in the area of MNP-assisted synthetic construction of aza- and oxa-heterocycles, published during the previous calendar year, 2022. The review serves as a valuable resource and also paves the way for future investigations in the development of novel catalytic strategies for heterocycle synthesis.1 Introduction2 Nanocatalysis3 Aza- and Oxa-Heterocycle Synthesis Catalysed by MNPs3.1 AuNPs3.2 CuNPs3.3 CoNPs3.4 FeNPs3.5 NiNPs3.6 PdNPs3.7 PtNPs3.8 SiNPs3.9 ZnNPs3.10 Bimetallic NPs3.11 Other MNPs4 Summary and Outlook

Moisture Recycling in the Colombian Andes

AbstractThe Colombian Andes (CA) are located over the northwestern corner of tropical South America (NW‐TropSA), where land and atmosphere interchange moisture and energy in a complex way owing to the orographic influence on the recycling of moisture over land. We aim to understand where and when water vapor evaporated from land turns into rainfall through moisture recycling, using the Water Accounting Model‐2layers (WAM‐2), an offline model to track atmospheric moisture forced with data from ERA‐5 at its native 0.25° resolution during 1980–2020. We define the spatiotemporal distribution of sources (high evaporation recycle ratios, ϵC) and receptors (high precipitation recycle ratios, ρC) of continental moisture at diverse timescales, including monthly, seasonal, annual and interannual (ENSO). Referring to the regional runs of WAM‐2 over NW‐TropSA (4°S–12°N/80°W–66°W), at elevations above 1,000 m.a.s.l., the CA has a mean annual ρC of 11% (ranging 6%–16%) and a mean annual ϵC of 35% (ranging 27%–40%). Moisture recycling in the CA exhibits a strong annual cycle over the region. The seasonal dynamic of moisture recycling shows two clear‐cut sources of moisture: the eastern foothills of the Eastern and Central ranges of the CA. Both foothills are also regions of high rainfall, although moisture recycling mechanisms differ. Sources of continental moisture grow spatially during September‐October‐November and March‐April‐May. The seasonal availability of moisture recycled coincides with regions where orography interacts with low level jets sourcing humidity. At interannual timescales, sources and receptors of continental moisture in the CA are modulated by the extreme phases of ENSO.

Multifunctional chitosan tailored γ-aluminum oxy-hydroxide monolith aerogels for sustained environmental remediation

Chitosan-tailored γ-AlOOH aerogels effectively remove dyes and heavy metals from water. With high recyclability and adsorption capacity, they offer an efficient, sustainable solution for industrial wastewater treatment.

Network topology diversification of porous organic salts.

Hydrogen-bonded organic frameworks (HOFs) are porous organic materials constructed via hydrogen bonds. HOFs have solubility in specific high-polar organic solvents. Therefore, HOFs can be returned to their components and can be reconstructed, which indicates their high recyclability. Network topologies, which are the frameworks of porous structures, control the pore sizes and shapes of HOFs. Therefore, they strongly affect the functions of porous materials. However, hydrogen bonds are usually weak interactions, and the design of the intended network topology in HOFs from their components has been challenging. Porous organic salts (POSs) are an important class of HOFs, are hierarchically constructed via strong charge-assisted hydrogen bonds between sulfonic acids and amines, and therefore are expected to have high designability of the porous structure. However, the network topology of POSs has been limited to only dia-topology. Here, we combined tetrasulfonic acid with the adamantane core (4,4',4'',4'''-(adamantane-1,3,5,7-tetrayl)tetrabenzenesulfonic acid; AdPS) and triphenylmethylamines with modified substituents in para-positions of benzene rings (TPMA-X, X = F, methyl (Me), Cl, Br, I). We changed the steric hindrance between the adamantane and substituents (X) in TPMA-X and obtained not only the common dia-topology for POSs but also rare sod-topology, and lon- and uni-topologies that are formed for the first time in HOFs. Changing template molecules under preparation helped in successfully isolating the porous structures of AdPS/TPMA-Me with dia-, lon-, and sod-topologies which exhibited different gas adsorption properties. Therefore, for the first time, we demonstrated that the steric design of HOF components facilitated the formation, diversification, and control of the network topologies and functions of HOFs.

Zeolite-encapsulated copper(II) complexes with NNO-tridentate Schiff base ligands: catalytic activity for methylene blue (MB) degradation under near neutral conditions.

Three novel copper Schiff base complexes, L1Cu(OAc)-L3Cu(OAc), bearing NNO tridentate ligands were synthesized and successfully entrapped in zeolite. All free and encapsulated complexes were fully characterized through experiments combined with theoretical calculations, and were subsequently employed as catalysts to activate H2O2 for degradation of methylene blue (MB). The catalytic activity of free complexes was tunable by substitution effects. The complex L3Cu(OAc) displayed enhanced efficiency by adopting bulky and donor substitutions due to the lower oxidation states. However, the free complexes exhibited modified structural and catalytic properties upon encapsulation into the zeolite. The constraint from the zeolite holes and coordination geometry caused the alteration of electronic structures and subsequently modified the reactivity. This study revealed that upon encapsulation, the larger molecular dimension of L3Cu(OAc) resulted in additional distorted geometry, leading to higher catalytic efficiency for MB degradation with more blue shifts in the UV-Vis spectrum. There was high catalytic activity by LnCu(OAc)-Y compared to that of the free complex, and high recyclability under near neutral conditions. In addition, the catalytic efficiency of L3Cu(OAc)-Y was higher or equivalent compared to other catalysts. This work provides new complexes with NNO tridentate ligands encapsulated inside zeolite and explains the relationship between the modified structure and functionality.

Engineering a polyvinyl butyral hydrogel as a thermochromic interlayer for energy-saving windows.

Achieving mastery over light using thermochromic materials is crucial for energy-saving glazing. However, challenges such as high production costs, limited durability, and recyclability issues have hindered their widespread application in buildings. Herein, we develop a glass interlayer made of a polyvinyl butyral-based hydrogel swollen with LiCl solution. In addition to a fast, isochoric, and reversible transparency-to-opacity transition occurring as ambient temperatures exceed thermally comfortable levels, this hydrogel uniquely encompasses multiple features such as frost resistance, recyclability, scalability, and toughness. The combination of these features is achieved through a delicate balance of polyvinyl butyral's amphiphilicity and the suppression of network-forming phase separation. This design endows a nanostructured polyvinyl butyral-LiCl composite gel with swollen molecular segments linked by dispersed cross-linking sites in the form of hydrophobic nano-nodules. Upon laminating this hydrogel (a thickness of 0.3 mm), the resultant glazing product demonstrates approximately 90% luminous transmittance even at sub-zero temperatures, along with a significant modulation of solar and infrared radiation at 80.8% and 68.5%, respectively. Through simulations, we determined that windows equipped with the hydrogel could reduce energy consumption by 36% compared to conventional glass windows in warm seasons. The widespread adoption of polyvinyl butyral in construction underscores the promise of this hydrogel as a thermochromic interlayer for glazing.

Quasi-2D MIL-100 (Fe) synthesis via benzene-1,3,5-tricarboxylic acid self-assembly: organic dye adsorption at room temperature with dramatically enhanced kinetics.

Amid increasing environmental pollution, two-dimensional materials have played pivotal roles in environmental remediation. However, two-dimensional metal-organic frameworks (2D-MOFs) have yet to be thoroughly explored. This study introduces a novel approach to synthesize 2D-MOFs, particularly focusing on MIL-100-(Fe), for the adsorption of emerging organic dyes. By harnessing the self-assembly of benzene-1,3,5-tricarboxylic acid (BTC), we formed thin solid interfaces of BTC as building blocks to control the growth of MIL-100-(Fe). This resulted in quasi-2D structures that showed over a 35% increase in adsorption capacity and a 5.5-fold increase in the adsorption kinetics of Rhodamine B removal compared to their 3D counterparts. This new method overcomes traditional synthesis limitations, offering a replicable and high-yield procedure for 2D-MOF synthesis. Compared to its three-dimensional counterpart (3D MIL-100 Fe), the prepared adsorbent exhibited remarkably higher efficacy in the adsorption of Rhodamine B, with high structural stability and recyclability. The prepared adsorbent shows over 99% adsorption within 90 minutes for initial dye concentrations of 1-40 mg L-1via the Langmuir adsorption mechanism and pseudo-second-order kinetics. Our research pioneers a method for the synthesis of quasi 2D-MIL-100-(Fe), laying the groundwork for fabricating other 2D-MOF structures, particularly those based on carboxylic acids.

Multivacant polyoxometalate-stabilizing palladium nanoparticles catalyze the N-formylation of amines with CO2 and H2

The multivacant POM-stabilizing Pd nanoparticles exhibited high efficiency and recyclability in the N-formylation reaction of amines with CO2 and H2.

Multifunctional MgAl LDH/Zn-MOF S-scheme heterojunction: efficient hydrogen production, methyl red removal, and CO2 adsorption

MgAl LDH/Zn-MOF S-scheme heterojunction exhibits superior photocatalytic activity for H2 evolution, methyl red dye removal and CO2 adsorption due to increased light absorption, high surface area, good stability and recyclability.

Heterogeneous solvent-metal-free aerobic oxidation of alcohol under ambient conditions catalyzed by TEMPO-functionalized porous poly(ionic liquid)s.

Heterogeneous solvent-metal-free aerobic oxidation of alcohols under ambient conditions is interesting but remains a significant challenge. Herein, a series of porous TEMPO-functionalized poly(ionic liquid)s (TEMPO-PILs) featuring a pure polycationic framework were successfully developed through the free radical polymerization of the ionic liquid 3-(2-chloroacetic acid-2,2,6,6-tetramethyl-1-oxo-4-piperidyl)-1-vinylimidazolium chloride and bis-vinylimidazolium bromide salt. Characterizations revealed that the obtained TEMPO-PILs possessed a high TEMPO density, abundant bromide ions, and a tunable porous structure, which enabled them to serve as solvent-free heterogeneous organocatalysts for the metal-free aerobic oxidation of benzyl alcohol under ambient conditions, exhibiting high catalytic activity and stable recyclability. A high yield of 99% coupled with a turnover frequency (TOF) of 13.3 h-1 was obtainable, which is higher than most of the reported TEMPO-based heterogeneous catalysts, even superior to homogeneous TEMPO-functionalized ionic liquids. Furthermore, a broad range of alcohols were effectively converted into their corresponding ketones and aldehydes. A possible reaction mechanism is proposed for understanding the catalytic oxidation behavior, indicative of the synergistic effect of TEMPO moieties and bromide ions.

A form-stable phase change material based on intermolecular hydrogen bonding with a high chemical recycling rate

A PEG-based FSPCM was prepared in water via a simple method, using mannitol as supporting material through intermolecular hydrogen bonding. This FSPCM has high latent heat values and can be chemically recycled with recycling rates over 90%.

Magnetically recoverable Fe3O4@SiO2@SBA-3@2-ATP-Cu: an improved catalyst for the synthesis of 5-substituted 1H-tetrazoles.

Functionalization of Fe3O4@SiO2@SBA-3 with double-charged 3-chloropropyltrimethoxysilane (CPTMS) and 2-aminophenol, followed by mechanical mixing of the solid product with copper(i) chloride produces a new, greener and efficient Fe3O4@SiO2@SBA-3@2-ATP-Cu catalyst for the synthesis of 5-substituted 1H-tetrazoles. XRD, SEM, atomic absorption, TGA, N2 adsorption-desorption, and VSM analyses were performed for the characterization of the Fe3O4@SiO2@SBA-3@2-ATP-Cu structure. Nitrogen adsorption-desorption analysis revealed that Fe3O4@SiO2@SBA-3@2-ATP-Cu has a surface area of 242 m2 g-1 and a total pore volume of 55.72 cm3 g-1. In synthesizing 5-substituted 1H-tetrazoles, Fe3O4@SiO2@SBA-3@2-ATP-Cu shows superior yields in short reaction times at 120 °C. This catalyst also showed high thermal stability and recyclability at least for 4 runs without apparent loss of efficiency.