Alternative Precursor Research Articles

A Facile Two-Step Utilization of Sorghum Waste Derived Activated Carbon

Sorghum (Sorghum bicolor (L.) Moench) is an agricultural commodity that produces waste, including stems, during its cultivation. Sorghum stems can be used as an alternative precursor for forming activated carbon (AC) with a high surface area by utilizing ZnCl2 as an activator and followed by a pyrolysis process at 750 °C under N2 gas. In this study, AC from sorghum stems was sequentially used as an adsorbent for heavy metals in wastewater, as well as applied as an anode material for lithium-ion batteries. From the characterization analysis, the synthesized AC has an amorphous structure, a high carbon content of > 90%, and a surface area of 1189 m2/g. AC was applied to adsorb 10, 50, and 100 ppm of metal cobalt (Co) at 30 °C. The adsorption isotherm and kinetics of metal Co showed an adsorption capacity of around 28.2 mg/g. The Langmuir isotherm model also describes Co adsorption and follows the pseudo-first-order equation. As for the Li-ion anode material, the ACs material is fabricated on a cylindrical battery with LiNi0.8Co0.1Mn0.1O2 as the counter cathode material. The specific discharge capacity results are 104 mAh/g at the voltage window of 2.7-4.3 V. The sequential utilization of sorghum stem-derived activated carbon can improve the product’s sustainability, and such an approach is promising to be applied in other biomass-based waste treatments.Keywords: Activated carbon, adsorption, battery, biomass, sorghum

The effect of copper slag as a precursor on the mechanical properties, shrinkage and pore structure of alkali-activated slag-copper slag mortar

Copper slag, an industrial by-product produced in large quantities during copper smelting and refining, has the potential to be used as an alternative precursor for alkali-activated materials. This approach not only reduces the environmental impact of copper slag but also addresses the growing scarcity of conventional precursors, such as ground granulated blast furnace slag. In this research, copper slag was used as an alternative precursor for alkali-activated slag-copper slag mortars. Sodium hydroxide and water glass served as the activators. The workability, mechanical properties, autogenous shrinkage and drying shrinkage were investigated to evaluate the influence of copper slag content. Furthermore, the reaction products and pore structure of hardened mortar were analysed to gain deeper insights into its performance. The results show that the incorporation of copper slag effectively prolongs the setting time and increases the fluidity. Copper slag reduces the autogenous shrinkage, but it also results in an undesirable increase in drying shrinkage. While copper slag delays strength development and reduces the strength, incorporating copper slag at a 50 % ratio still results in strength comparable to that of mortars utilizing 100 % ground granulated blast furnace slag as the precursor. The incorporation of copper slag alters the composition of calcium aluminosilicate hydrate and promotes the formation of ferro-silicate. Although it reduces the proportion of macropores in the total pore volume, it simultaneously increases the amount of capillary pores. Copper slag alters pore solution, and although heavy metal leaching remains minimal, risks in complex environments require further study.

Nitrogen‐Induced Microcrystalline‐to‐Nanocrystalline Structure Transition in Diamond Films Grown by Microwave Plasma Chemical Vapor Deposition: Comparison of N2 and NH3 Precursors

The structure and properties of polycrystalline chemical vapor deposition (CVD) diamond coatings grown by microwave plasma CVD in H2–CH4 mixtures can be effectively controlled by nitrogen admixture in the process gas. Here, a comparative study of adding nitrogen from different precursors, N2 and ammonia NH3, in concentrations up to 0.4%vol on grain size, texture, surface roughness, and sp2/sp3 ratio of the produced films on Si substrates is performed. A transition from microcrystalline to smooth nanocrystalline diamond structure is found to occur at a certain concentration of the precursor, for NH3 this threshold concentration being much lower, 0.02–0.1%, than for N2. The higher activity of ammonia is associated with easier formation of cyano radicals in the plasma as detected with optical emission spectroscopy, in accord with the lower bond‐dissociation energy for NH3 compared to N2. On the contrary, a smaller addition (0.004%) of either N2 or NH3 promotes almost doubling of the growth rate, while preserving the microcrystalline structure of the film. The results establish ammonia as a convenient alternative precursor to commonly used N2 added in the plasma for the diamond film structure modifications.

Optimizations of Liquid Phase Deposition Processes for Enhanced Photoelectrocatalytic Activities of Tungsten Oxide Thin Films.

This study focuses on the preparation of tungsten oxide (WO3) as the photoanode for water oxidations by the liquid phase deposition (LPD) technique and its optimizations to improve the photoelectrochemical performance. The alternative precursor large stock solution process was achieved to simplify the LPD process for WO3 thin film preparation. The effect of boric acid in the precursor solutions on the physicochemical properties of the deposited WO3 thin films was investigated. As a result, we found that the optimized concentration of boric acid realized the highest photoelectrochemical performance. Through the optimizations of reaction conditions and surface analyses, we concluded that the preparations of a semiconductor film via the LPD technique had the potential to obtain high-performance photoelectrocatalytic applications.

Simultaneously improving the strength and ductility of an oxide dispersion-strengthened high-entropy alloy by employing innovative precursors for oxide formation

The engineering of a composite microstructure, achieved by coupling heterogeneous grain distribution with oxide dispersion, has been demonstrated as an effective strategy for enhancing the strength-ductility synergy of alloys at both room and elevated temperatures. The effectiveness of this approach is strongly correlated with the micro-features of dispersed oxides. In this study, we selected the Ni38Co20Cr20Fe18Ti4 high-entropy alloy (HEA) as the base material, which could achieve the desired composite structure through preparation using mechanical alloying and spark plasma sintering methods. Our primary objective was to investigate the effects of incorporating Y2O3 or utilizing hydrides (TiH2 and YH3) as alternative precursors on the modification of oxide precipitates, evolution of a bimodal grain microstructure, and alteration in mechanical properties for the oxide dispersion strengthened (ODS) HEA. The results show that the incorporation of Y2O3 promotes the formation of ultrafine and semi-coherent Y2Ti2O7 ternary oxide particles, in addition to the pre-existing coarse binary TiO in the HEA matrix. Moreover, this leads to a significant increase in the fraction and a decrease in the average size of ultrafine grains (UFGs) within the bimodal microstructure. Notably, utilizing Ti- and Y-hydrides instead of Y2O3 and Ti as oxide-forming precursors within an equivalent composition remarkably amplifies the precipitation proportion of Y2Ti2O7 among dispersoids while further refining UFGs. The ODS-HEA synthesized using hydrides exhibits a simultaneous enhancement of 12 % in yield strength and 13 % in elongation to fracture, compared to that prepared from Ti and Y2O3. This intriguing phenomenon primarily arises from the heightened strengthening and toughening contributions, facilitated by the increased precipitation of advantageous Y2Ti2O7 nanoparticles.

Early-age structural build-up and rheological assessment of alkali-activated slag-red clay brick waste pastes: Influence of silica modulus and precursors proportions

Sustainability plays a crucial role in the current context of the cement industry, and alkali-activated materials (AAMs) are emerging as eco-efficient alternative binders. On the other hand, the massive generation of red brick waste worldwide and its lack of a defined destination emphasizes this material as an alternative precursor that has been insufficiently explored in the literature. Based on this context, the present study aims to investigate the structural build-up, reaction kinetics, and rheological properties of alkali-activated pastes based on blast furnace slag (BFS) and red clay brick waste (RBCW). Fresh properties such as structural build-up, rheology, and reaction kinetics are lacking in the literature on RCBW-based AAMs, highlighting these properties as a research gap to be filled and discussed in depth in this paper. The flow sweep test was performed, linked to yield stress and viscosity properties. The structural build-up was evaluated by strain sweep and small amplitude oscillatory shear (SAOS) tests based on viscoelastic parameters: storage modulus, loss modulus, and phase angle. Isothermal calorimetry and in-situ FTIR were also conducted to complement the analysis and provide insight into the reaction kinetics, chemical structure, and product formation. Higher silica modulus (Ms) resulted in a lower structural build-up rate and a delayed reaction. Higher content of RCBW resulted in a delayed structuration process, which was linked to a delay in the precipitation of aluminosilicate gels. Early increase in the structural build-up in 25 % and 50 % RCBW blends (Ms = 1.0) is associated with the early formation of a well-percolated network.

Engineering a non-oxidative glycolysis pathway in escherichia coli for high-level citramalate production

BackgroundMethyl methacrylate (MMA) is a key precursor of polymethyl methacrylate, extensively used as a transparent thermoplastic in various industries. Conventional MMA production poses health and environmental risks; hence, citramalate serves as an alternative bacterial compound precursor for MMA production. The highest citramalate titer was previously achieved by Escherichia coli BW25113. However, studies on further improving citramalate production through metabolic engineering are limited, and phage contamination is a persistent problem in E. coli fermentation.ResultsThis study aimed to construct a phage-resistant E. coli BW25113 strain capable of producing high citramalate titers from glucose. First, promoters and heterologous cimA genes were screened, and an effective biosynthetic pathway for citramalate was established by overexpressing MjcimA3.7, a mutated cimA gene from Methanococcus jannaschii, regulated by the BBa_J23100 promoter in E. coli. Subsequently, a phage-resistant E. coli strain was engineered by integrating the Ssp defense system into the genome and mutating key components of the phage infection cycle. Then, the strain was engineered to include the non-oxidative glycolysis pathway while removing the acetate synthesis pathway to enhance the supply of acetyl-CoA. Furthermore, glucose utilization by the strain improved, thereby increasing citramalate production. Ultimately, 110.2 g/L of citramalate was obtained after 80 h fed-batch fermentation. The citramalate yield from glucose and productivity were 0.4 g/g glucose and 1.4 g/(L·h), respectively.ConclusionThis is the highest reported citramalate titer and productivity in E. coli without the addition of expensive yeast extract and additional induction in fed-bath fermentation, emphasizing its potential for practical applications in producing citramalate and its derivatives.

An NMR study on the keto-enol tautomerism of 1,3-dicarbonyl drug precursors.

The effective implementation of drug precursor legislation has driven the innovation and design of new alternative substances. The application of 1,3-dicarbonyl precursors as alternative precursors for the synthesis of 1-phenyl-2-propanone (P2P) and 3,4-methylenedioxyphenyl-2-propanone (MDP2P) has created new challenges to legal control. Their 1,3-dicarbonyl structure allows the precursors to exist as an equilibrium mixture of the tautomeric diketo and keto-enolic forms during the nuclear magnetic resonance (NMR) analysis. In this study, the keto-enol tautomerism of four 1,3-dicarbonyl drug pre-precursors, α-phenylacetoacetamide (APAA), methyl α-phenylacetoacetate (MAPA), ethyl α-phenylacetoacetate (EAPA), and methyl 2-(benzo[d][1,3]dioxol-5-yl)-3-oxobutanoate (MAMDPA) were investigated through NMR. One-dimensional (1D) and 2D NMR were combined to assign signals for the diketo and keto-enolic tautomers. Results showed that the keto-enol tautomerism was solvent-dependent but was also influenced by the substituent present in the molecule. Further, the analysis results indicated that majority of substances existed mainly in the diketo form. The enol-keto equilibrium constant (Keq) was stable in dimethyl sulfoxide-d6 and chloroform-d, while unstable for some compounds in acetone-d6 and deuterated methanol. The presence of impurities in the seized sample may disrupt the equilibrium between keto-enol tautomers in 1,3-dicarbonyl precursors. After the optimization of several key quantitative parameters, a quantitative NMR method for the quantification of 1,3-dicarbonyl drug precursors were also developed to facilitate their quantitative analysis. This is the first study to investigate the keto-enol tautomerism and quantification of 1,3-dicarbonyl drug precursors by NMR, providing a new approach for structure analysis and quantification of new precursor analogues.

(Invited) Low Temperature Atomic Layer Deposition Processes for Large-Area Synthesis of 2D Transition Metal Dichalcogenides

2D materials have been the focus of intense research in the last decade due to their unique physical properties. This presentation will highlight our recent progress on the large-area synthesis of two-dimensional transition metal chalcogenides for nanoelectronics using advanced atomic layer deposition cycle schemes. First, how we can use advanced cycle schemes to deposit wafer-scale polycrystalline MoS2 thin films at very low temperatures down to 100 °C. We have identified the critical role of hydrogen during the plasma step in controlling the composition and properties of molybdenum sulfide films. By increasing the H2/H2S ratio or adding an extra hydrogen plasma step to our ALD process, we are able to deposit pure polycrystalline MoS2 films at temperatures as low as 100 °C. To the best of our knowledge, this represents the lowest temperature for crystalline MoS2 films prepared by any chemical gas-phase method.[1]The most dominant methods for preparing MoS2 via ALD is to alternately expose a substrate to a metalorganic precursor and a hydrogen sulfide (H2S) or a plasma containing H2S. H2S is a corrosive, toxic, and flammable gas that is heavier than air, which makes it hazardous and expensive to store, install, and transport. Alternative sulfur precursors in the solid or liquid phase would be beneficial in terms of cost and safety and would require the installation of no additional hardware for most ALD reactors. In the second half of this contribution, the widely researched ALD process using bis(tert-butylimido)bis(dimethylamino)molybdenum(IV) ((tBuN)2(NMe2)2Mo) and H2S plasma is compared to a novel ALD process using (tBuN)2(NMe2)2Mo, hydrogen plasma, and di-tert-butyl disulfide (TBDS), which is an inexpensive, liquid-phase sulfur precursor.[1] M. Mattinen et al., Chem. Mater. (2022), 34, 5104

Manganese-catalyzed cyclopropanation of allylic alcohols with sulfones

Cyclopropanes are among the most important structural units in natural products, pharmaceuticals, and agrochemicals. Herein, we report a manganese-catalyzed cyclopropanation of allylic alcohols with sulfones as carbene alternative precursors via a borrowing hydrogen strategy under mild conditions. Various allylic alcohols and arylmethyl trifluoromethyl sulfones work efficiently in this borrowing hydrogen transformation and thereby deliver the corresponding cyclopropylmethanol products in 58% to 99% yields. Importantly, a major benefit of this transformation is that the versatile free alcohol moiety is retained in the resultant products, which can undergo a wide range of downstream transformations to provide access to a series of functional molecules. Mechanistic studies support a sequential reaction mechanism that involves catalytic dehydrogenation, Michael addition, cyclization, and catalytic hydrogenation.

Electroless Deposition of Noble Metals on Rod-Shape Plant Viruses in Various Aqueous Metal Precursor Solutions.

The challenge of synthesizing noble metal nanostructures sustainably has encouraged researchers to explore biological routes for nanostructure production, such as biotemplating. Plant viruses with rod-shape morphology, such as tobacco mosaic virus (TMV) and barley stripe mosaic virus (BSMV), offer promising biotemplates to produce metal nanorods. TMV and BSMV can be incubated in aqueous metal precursor solutions to mineralize metals on the coat proteins (CPs) of the viruses. Previous studies have primarily examined palladium (Pd) mineralization on TMV and BSMV using Na2PdCl4 as the Pd precursor. There is limited scientific literature on the effect of using alternative Pd precursor solutions besides Na2PdCl4 such as K2PdCl4 and PdCl2 to mineralize Pd on TMV and BSMV. Past attempts at mineralizing other noble metals such as platinum (Pt) and gold (Au) required an initial layer of Pd to be deposited on the TMV and BSMV biotemplates. In this study, we aimed to expand the understanding of using alternative Pd precursor solutions to mineralize Pd on TMV and BSMV. Additionally, the deposition of Pt and Au onto TMV and BSMV without the need for an initial Pd mineralization layer was achieved using alternative Pt and Au precursors, including K2PtCl4 and AuCl3, respectively. Pd, Pt, and Au were successfully deposited on TMV and BSMV by incubation in aqueous solutions of Na2PdCl4, K2PdCl4, PdCl2, K2PtCl4, and AuCl3. Kinetic studies were also conducted using ultraviolet-visible (UV-vis) spectroscopy to examine the rates at which Pd, Pt, and Au precursor ions were reduced during the mineralization process, mimicking their adsorption onto TMV and BSMV CPs. BSMV adsorbed noble metal precursor ions faster than TMV as determined by UV-vis spectroscopy. While palladium nanorods (PdNRs) offer high electrical conductivity desirable for electronic applications, Pd-coated TMV and BSMV may face limitations due to their organic cores, potentially compromising conductivity. To address this, one approach is to convert the organic core into conductive amorphous carbon through thermal annealing. In this study, in situ transmission electron microscopy was utilized to thermally anneal Pd-TMV2Cys, thereby transforming them into PdNRs with amorphous carbon cores.

Thermal activation of kaolinite through potassium acetate intercalation: A structural and reactivity study

Calcined clays have emerged as a suitable alternative to partially replace conventional cement due to their high pozzolanic activity. This study explores a novel activation methodology for kaolinite, aiming to obtain metakaolin at lower temperatures than conventional thermal activation. This methodology involves a prior intercalation stage with potassium acetate (KAc) before thermal activation. The effectiveness of KAc intercalation was assessed through X-ray diffraction (XRD), indicating an intercalation ratio of approximately 90%. Several calcined temperatures were tested in accordance with the thermal behaviour analyzed through thermogravimetric analysis (TGA). Once calcined, the intercalated kaolinites exhibited enhanced reactivity compared to conventional calcined clays in the range between 400 °C to 550 °C, as demonstrated by modified Chapelle and Si/Al availability tests. A comprehensive structural characterization was conducted to facilitate a better understanding of the novel KAc-based metakaolin reactivity through various techniques (XRD, 27Al - 1H MAS NMR, and TGA). This focused on the crystalline changes in the kaolinite structure, the evolution of Al atoms conformation, and the OH behaviour at different thermal activation temperatures. Overall, this study highlights the potential of KAc intercalation as a strategy to obtain higher metakaolin content at lower temperatures than through conventional thermal treatments, offering insights into the development of its potential use as supplementary cementitious materials or alternative cementitious materials precursor.

WITHDRAWN: From Debris to Innovation: Unveiling a New Frontier for Alkali-Activated Materials

Alkali-activated materials (AAMs) play a crucial role in addressing the environmental challenges of traditional construction binders by offering a lower carbon footprint alternative. Industrial by-products are utilized, reducing waste and energy consumption associated with lime and cement production. AAMs represent a sustainable innovation in the construction industry, promising significant reductions in CO2 emissions and resource utilization. This review aims to meticulously analyze the existing body of research on the potential of Construction and Demolition Waste (CDW) as an alternative precursor for producing AAMs. This review study introduces a novel angle by critically evaluating advancements in CDW processing techniques for AAM production, alongside assessing the environmental and mechanical outcomes. It pioneers bridging the gap between innovative recycling methods and sustainable construction practices. The ultimate goal is to synthesize findings into a comprehensive framework to guide future research toward optimizing CDW utilization in AAM production, thereby contributing to sustainable construction practices and the circular economy. This study stands out for its in-depth examination of CDW's role in mitigating the environmental impact of conventional construction materials, offering novel insights into the path toward sustainability in the construction industry. By critically assessing the latest advancements in CDW processing techniques and their environmental and mechanical implications, the study not only underscores the potential of CDW in revolutionizing the construction industry but also sets a new precedent in sustainability research. It bridges the crucial gap between theoretical innovation and practical application, offering actionable insights for optimizing CDW utilization in AAM production. This comprehensive analysis signifies a pivotal step towards integrating sustainable practices within the construction sector, advocating for a paradigm shift towards a circular economy that prioritizes resource efficiency and environmental stewardship.

Basic oxygen furnace (BOF) slag as an additive in sodium carbonate-activated slag cements

Basic oxygen furnace slag (BOFS) is a high-volume waste resulting from the production of steel from pig iron. Due to its high free lime content, BOFS is difficult to recycle and/or include into conventional cement systems. Alkali-activation technology offers a pathway to transform industrial wastes such as BOFS into low-carbon cements. Alternative precursors for cement systems are needed as the reliance on commonly used materials like ground granulated blast furnace slag (GGBFS) is becoming unsustainable due to decreasing availability. This study investigates alkali-activated cements incorporating 20 and 30 wt.% of naturally weathered BOFS as a replacement for GGBFS, in both sodium silicate- and sodium carbonate-activated systems. A fraction of BOFS subject to mechanical activation is compared against the untreated BOFS in the 20 wt.% systems. It is observed that in naturally weathered BOFS, a significant portion of the free-lime is found to convert to portlandite, which accelerates alkali-activation kinetics. In sodium silicate-activated systems, the high pH of the activator results in incomplete reaction of the portlandite present in BOFS. The sodium carbonate-activated system shows near complete conversion of portlandite, causing an acceleration in the kinetics of reaction, setting, and hardening. These findings confirm the viability of sodium carbonate activated GGBFS-based systems with only a minor loss in strength properties. BOFS can be utilised as a valuable cement additive for the production of sustainable alkali-activated cements utilising sodium carbonate as a less carbon-intensive activator solution than the more commonly used sodium silicate. Mechanical activation of BOFS offers further optimisation potential for alkali-activation.

The Utilisation of Rice Husk Ash Leachates for The Synthesis of Eco-Friendly Geopolymers

Geopolymers are inorganic polymers projected as feasible alternatives to Portland cement due to their lower CO2 emissions and high mechanical properties. In recent times, however, their impact on other environmental indices such as abiotic depletion, freshwater toxicity, marine ecotoxicity, terrestrial ecotoxicity, acidification, and human toxicity has become questionable, thus the need to investigate alternative eco-friendly precursors and activators. This work aims to manufacture an eco-efficient geopolymer by utilising biomass ash leachate as an alternative to the conventional alkali silicate solution. The leachate was obtained by soaking the rice husk ash (RHA) in a 10 M concentration of NaOH solution and filtering to obtain a clear solution. The effects of the calcination temperature of the kaolin and the RHA content in the alkaline solution were investigated, and a factorial design of experiments was developed considering three levels of calcination temperature (700°C, 800°C, and 900°C) and five levels of RHA content (0 g, 5 g, 10 g, 15 g, and 20 g). Physical and mechanical tests were performed on the synthesised geopolymer pastes, and chemical analysis was performed using X-ray diffraction and X-ray spectroscopy. The impacts of replacing the synthetic alkali silicates with rice husk ash-based activators were compared. The results showed that the calcination temperature of the kaolin and the content of the RHA both contributed significantly to the flexural and compressive strength at the 0.01 level of significance. A compressive strength of 10.4 MPa was obtained for the MK915 binders, which showed a 100% increase from samples without RHA content. This research proves that utilising RHA-based activators in metakaolin-based geopolymers can be feasible for less critical applications where a very high compressive strength will not be required.Keywords: alkaline activators, biomass, geopolymers, leachates, rice husk ash

Magnesium vs. sodium alginate as precursors of calcium alginate: Mechanical differences and advantages in the development of functional neuronal networks

Calcium alginate is one of the most widely employed matrices in regenerative medicine. A downside is its heterogeneity, due to the poorly controllable character of the gelation of sodium alginate (NaAlg), i.e. the commonly used alginate salt, with calcium. Here, we have used magnesium alginate (MgAlg) as an alternative precursor of calcium alginate. MgAlg coils, more compact and thus less entangled than those of NaAlg, allow for an easier diffusion of calcium ions, whereas Mg is exchanged with calcium more slowly than Na; this allows for the formation of a material (Ca(Mg)Alg) with a more reversible creep behaviour than Ca(Na)Alg, due to a more homogeneous – albeit lower - density of elastically active cross-links. We also show that Ca(Mg)Alg supports better than Ca(Na)Alg the network development and function of embedded (rat cortical) neurons: they show greater neurite extension and branching at 7 and 21 days (Tubb3 and Map2 immunofluorescence) and better neuronal network functional maturation / more robust and longer-lasting activity, probed by calcium imaging and microelectrode array electrophysiology. Overall, our results unveil the potential of MgAlg as bioactive biomaterial for enabling the formation of functional neuron-based tissue analogues.

Adsorption of dimethylaluminum isopropoxide (DMAI) on the Al2O3 surface: A machine-learning potential study

Dimethylaluminum isopropoxide (DMAI) is attracting attention as an alternative precursor for atomic layer deposition (ALD) of aluminum oxide (Al2O3). However, the surface chemical reaction mechanisms of DMAI during ALD regarding its dimeric structure under vacuum deposition process conditions has yet to be clear. In this work, the adsorption mechanism of dimeric and monomeric DMAI on a fully hydroxylated Al2O3 surface is studied using machine-learning potential (MLP) calculations. The initial adsorption of DMAI appears facile and would result in the coexistence of both methyl and isopropoxy ligands on the surface. The reactivity of DMAI is smaller than that of TMA, owing to the propensity of DMAI to adopt a dimeric form. Especially when the substrate is partially covered by other adsorbate species, the large molecular size and low reactivity of dimeric DMAI considerably hinder its reactivity toward surface adsorption. Current results are in good correspondence with the previous experimental results, where lower growth per cycle (GPC) and higher selectivity in area-selective ALD (AS-ALD) could be observed by using DMAI than compared to those of TMA processes.

Functional properties and continuous adsorption process of Arenga pinnata shell and its porous biochars for aqueous methylene blue removal

Arenga pinnata shell, an agricultural-processing residue, was used as an alternative precursor for synthesizing Arenga pinnata shell particles (ASP), Arenga pinnata shell biochar (ASB), and Arenga pinnata shell activated biochar (ASAB) for methylene blue (MB) adsorption. Optimized adsorbent was observed for ASAB fabricated via an impregnation ratio of KOH to ASP of 0.5:1 (w/w) at 700 °C for 30 min of activation time under N2 pyrolysis, with a surface area, pore volume, and average pore diameter of 967 m2/g, 0.572 cm3/g, and 2.47 nm, respectively. The adsorbent also possesses the largest carbon constituent (90.4 %), negative surface charge (−36.4 mV), and abundant oxygen-containing functional groups. Dynamic MB adsorption properties on the adsorbents from the aqueous environment under continuous mode at 25 °C were determined using the Thomas and Yoon-Nelson models. Although the ASP and ASB presented comparatively favorable adsorption properties, the optimum adsorption performance was observed for the ASAB. Its superior functional features contributed to the largest adsorption capacity of 203.86 mg/g. The elemental composition analysis indicated the presence of sulfur on the ASAB surface, which supported the findings. This research demonstrates the utility of Arenga pinnata shell as an eco-friendly precursor for high-performance adsorbent fabrication with excellent MB adsorption properties.

Who is Who in the Carbene Chemistry of N‐Sulfonyl Hydrazones

Comprehensive SummaryOver the past few decades, N‐sulfonyl hydrazones have been recognized as alternative precursors for hazardous diazo compounds in organic synthesis, allowing for diverse innovative and original chemical transformations that were otherwise difficult to achieve. This critical review summarizes the major advancements in the carbene chemistry of N‐sulfonyl hydrazones. The contents of this review are organized based on research conducted by leading scientists who have made significant contributions to this field. The individual carbene transfer reactions and their mechanisms, as well as the potential applications in the synthesis of natural products and complex bioactive molecules, are thoroughly discussed.

Light Induced Cobalt(III) Carbene Radical Formation from Dimethyl Malonate As Carbene Precursor.

Radical-type carbene transfer catalysis is an efficient method for the direct functionalization of C-H and C=C bonds. However, carbene radical complexes are currently formed via high-energy carbene precursors, such as diazo compounds or iodonium ylides. Many of these carbene precursors require additional synthetic steps, have an explosive nature, or generate halogenated waste. Consequently, the utilization of carbene radical catalysis is limited by specific carbene precursors that access the carbene radical intermediate. In this study, we generate a cobalt(III) carbene radical complex from dimethyl malonate, which is commercially available and bench-stable. EPR and NMR spectroscopy were used to identify the intermediates and showed that the cobalt(III) carbene radical complex is formed upon light irradiation. In the presence of styrene, carbene transfer occurred, forming cyclopropane as the product. With this photochemical method, we demonstrate that dimethyl malonate can be used as an alternative carbene precursor in the formation of a cobalt(III) carbene radical complex.