Synthesis Of Materials Research Articles

Activated carbon from waste fabrics as a catalyst for NaBH4 methanolysis

Hydrogen energy is attractive as a sustainable and clean energy. Chemical hydrides are being studied as a solution to the transportation and storage problems of hydrogen. Hydrogen can be produced by methanolysis reaction of sodium borohydride on a suitable catalyst. For this purpose, metal catalysts with high catalytic activity are generally used. Despite their high catalytic activity, the environmental impact and cost of metal-containing catalysts has led to increased interest in synthesizing metal-free catalysts. Activated carbons are advantageous materials for metal-free catalyst applications. In recent years, industrial wastes have attracted much attention for the synthesis of sustainable materials for activated carbon preparation. In this study, activated carbons are produced from waste fabrics by chemical activation method using H3PO4 and KOH chemical agents at different impregnation ratios (1:1, 2:1 and 3:1 % w:w) and different carbonization temperatures (400, 500, 600°C for H3PO4 and 600, 700, 800°C for KOH). These carbons are used as catalysts for hydrogen production and their catalytic activity is evaluated based on hydrogen generation rate (HGR). Therefore, the effect of different conditions used in the preparation of activated carbon was investigated to determine its impact on HGR. The increase in carbonization temperature decreases the HGR value of the catalyst. The increase in acid concentration increases the HGR value. The highest HGR value is obtained as 39600 mL/(min.gcat) with YKK1–800 activated carbon. Once the carbon with high activity is identified, the effect of reaction conditions such as NaBH4, methanol, catalyst amount, and temperature on HGR is investigated. The catalytic activities of the prepared activated carbons in NaBH4 electrooxidation are also investigated. YKK3–700 activated carbon shows the highest catalytic activity at 1.91 mA/cm2 at −0.63 V peak potential. This result is promising for the use of metal-free catalysts for direct sodium borohydride fuel cells.

Hybrid deterministic and stochastic approach for dynamic simulation of photoinduced atom-transfer radical polymerization processes with microscopic resolution

Among the various polymerization mechanisms available for producing polymers, photoinduced atom-transfer radical polymerization (photoATRP) stands out as a promising technique. By utilizing light as an external stimulus, photoATRP facilitates the production of well-defined polymers with precise distributions. The demand for advanced polymeric materials synthesis necessitates a deep understanding of polymer chains at the molecular level. As molecular weight distribution (MWD) is a key quality index of polymers, developing models with embedded MWD information holds significance for process design and optimization tasks. In this work, an accelerated hybrid deterministic and stochastic approach is proposed for simulating dynamic photoATRP processes. The proposed approach demonstrates computational efficiency and flexibility, enabling precise predictions for the evolution of both macroscopic and microscopic properties of polymers. An application to a batch photoATRP system model is presented to illustrate the validity and performance of the proposed hybrid approach.

Fracture-Resistant Stretchable Materials: An Overview from Methodology to Applications.

Stretchable materials, such as gels and elastomers, are attractive materials in diverse applications. Their versatile fabrication platforms enable the creation of materials with various physiochemical properties and geometries. However, the mechanical performance of traditional stretchable materials is often hindered by the deficiencies in their energy dissipation system, leading to lower fracture resistance and impeding their broader range of applications. Therefore, the synthesis of fracture-resistant stretchable materials has attracted great interest. This review comprehensively summarizes key design considerations for constructing fracture-resistant stretchable materials, examines their synthesis strategies to achieve elevated fracture energy, and highlights recent advancements in their potential applications.

Synergistic bimetallic nanozymes of Ni/ZIF-8 and Cu/ZIF-8 as carbonic anhydrase mimics

The remarkable diversity of metal nodes and ligands, coupled with the extensive array of connection modes, enables the precise design and assembly of metal-organic frameworks (MOFs), which have garnered significant attention in the field of nanozyme. In this study, the synthesis of zeolite imidazole framework materials (ZIFs) with varying Zn2+ and Ni2+ or Cu2+ concentrations were investigated and regulated by methanol, aiming to mimic the CO2 hydration activity of carbonic anhydrase (CA). The materials were comprehensively characterized using TEM, XRD, FTIR, UV-Vis DRS, XPS, and subsequently the catalytic performance of the materials was assessed. The results demonstrated that the structural characteristics of bimetallic Ni/ZIF-8 and Cu/ZIF-8 were influenced by varying concentrations of metal ions. Notably, ZIF-8 doped with lower metal content exhibited enhanced stability, while a precursor containing nickel and copper ions exceeding 50% hindered the formation of the desired ZIFs, resulting in an unstable cluster structure. However, methanol can counteract the inhibitory effect of metal ions on the structure. The bimetallic synergies of doped metals in ZIFs CA mimics can simultaneously expedite both two rate-limiting steps in the CO2 hydration process. The esterase activity of ZIF-8 doped with a small quantity of Ni2+ or Cu2+ can be achieved at a level comparable to that of human carbonic anhydrase (hCA II) at 80 °C, along with remarkable catalytic performance and hydrothermal stability. Specifically, Cu66%/ZIF-8 exhibited an activity of 0.31 U·mg−1 at 25 °C, which was 2.31 times higher than that of ZIF-8, moreover, the esterase activity at 80 °C was approximately 2.21 times greater than that of ZIF-8 under the same condition. While the relative activity of Ni50%/ZIF-8 and Cu50%/ZIF-8 still exceeding 50% even after five repeated utilization cycles. The bimetallic Ni/ZIF-8 and Cu/ZIF-8 can be easily synthesized using a simple method, resulting in enhanced catalytic activity. Therefore, it holds great potential for future applications in CO2 capture.

Electrochemiluminescence detection of diazinon in vegetables based on the synergistic interaction of WO3-x dots with Au@SiO2 nanocapsules

In this work, a simple synthesis of low-toxicity transition metal material of WO3-x dots was used as a co-reactant with Au@SiO2 as a core-shell material and a signal amplification factor to collaboratively promote Ru(bpy)32+ electrochemiluminescence (ECL) for the construction of a highly sensitive aptasensor for the detection of diazinon (DZN) in vegetables. Electrodes modified with multi-walled carbon nanotubes-chitosan composite membranes (MWCNTs-CS) were used to load and immobilize more Ru(bpy)32+.can load more Ru(bpy)32+. WO3-x dots synthesized by a simple method showed excellent ECL efficiency as a novel co-reactant for Ru(bpy)32+. Under optimized conditions, this aptasensor for DZN has a wide detection range (10 pg mL−1 - 1 μg mL−1.) and a low detection limit (0.0197 ng L−1). The aptasensor has shown good results in the analysis of real samples in the experiment. This work provides a new approach to the construction of a novel electrochemiluminescence sensor for the detection of pesticides.

Reductive Segregation During the Synthesis of Sb−SnO2-Supported Iridium Electrocatalysts for the Oxygen Evolution Reaction

A metal-organic chemical deposition approach using an Ir(acac)3 precursor was employed to synthesise oxide−supported iridium-based electrocatalysts for the oxygen evolution reaction (OER) in acidic media. Inert and oxidising deposition conditions were explored in two temperature regimes, and the influence of these parameters on the physicochemical and electrochemical properties of catalysts consisting of IrOx supported on Sb–SnO2 (ATO) were studied. Surprisingly, it was found that increasing the deposition temperature up to 620 °C favoured the formation of reduced iridium phases even in the presence of an oxidising reaction environment. This was explained by a thermodynamic preference for reduced phases at high temperatures, as well as the presence of acetylacetonate ligand decomposition products serving as reducing agents. Similarly, the reductive segregation of Sb from the ATO support at high temperatures leads to the loss of conductivity of the support, and the formation of Ir–Sb–Sn alloyed nanoparticles. These processes resulted in a loss of OER performance for the materials prepared under high-temperature conditions. Our findings highlight the importance of carefully selecting the temperature range during the synthesis of oxidic support materials and electrocatalysts for the OER.

A Transparent and Injectable Biomaterial Prepared by Mixing Collagen and Anti-Cancer Platinum Derivatives.

This study presents the synthesis of a cross-linked collagen material, named platinum-containing collagen gel (PCG), which is achieved by simply mixing collagen and derivatives of an anti-cancer platinum complex. The cross-linking reagents are derivatives of cisplatin or transplatin, generated through a ligand exchange with dimethyl sulfoxide. PCG exhibits superior physical strength and transparency compared with the native collagen gel formed through spontaneous fibril formation. The versatility of PCG as a cell culture scaffold, applicable to both 2D and 3D models, with low cytotoxicity is demonstrated. Furthermore, PCG exhibits pH-responsive gel-forming properties. This enables the removal of free cross-linker by dialysis in an acidic solution and subsequent gel formation upon neutralization. This material holds promise for application in cell culture scaffolds and medical injections.

Spray drying synthesis of perspective materials for cathodes of Li-ion batteries

Spray drying synthesis of perspective materials for cathodes of Li-ion batteries

Calcium‐dependent antimicrobials: Nature‐inspired materials and designs

AbstractBacterial infection remains a major complication answering for the failures of various implantable medical devices. Tremendous extraordinary advances have been published in the design and synthesis of antimicrobial materials addressing this issue; however, the clinical translation has largely been blocked due to the challenge of balancing the efficacy and safety of these materials. Here, calcium's biochemical features, natural roles in pathogens and the immune systems, and advanced uses in infection medications are illuminated, showing calcium is a promising target for developing implantable devices with less infection tendency. The paper gives a historical overview of biomedical uses of calcium and summarizes calcium's merits in coordination, hydration, ionization, and stereochemistry for acting as a structural former or trigger in biological systems. It focuses on the involvement of calcium in pathogens’ integrity, motility, and metabolism maintenance, outlining the potential antimicrobial targets for calcium. It addresses calcium's uses in the immune systems that the authors can learn from for antimicrobial synthesis. Additionally, the advances in calcium's uses in infection medications are highlighted to sketch the future directions for developing implantable antimicrobial materials. In conclusion, calcium is at the nexus of antimicrobial defense, and future works on taking advantage of calcium in antimicrobial developments are promising in clinical translation.

NH4Cl-assisted synthesis of TaON nanoparticle applied to photocatalytic hydrogen and oxygen evolution from water

Oxynitride semiconductors are promising photocatalyst materials for visible light-driven water splitting, while the synthesis of well crystalized oxynitride still remains challenge. In present work, narrow-bandgap TaON nanoparticles are synthesized via heating a vacuum-sealed mixture of KTaO3, Ta and NH4Cl. This method possesses multiple advantages in terms of lower calcination parameter, higher N conversion efficiency and superior photocatalytic activity in comparison with the traditional thermal ammonolysis using NH3 gas as a nitrogen source. Through the analysis of intermediates produced upon the elevation of heating temperature, a gas–solid-phase reaction between TaCl5 and Ta2O5 is demonstrated as the final step, which is conducive to decreasing thermal energy barrier and accelerating nitridation process. Precise control of preparation conditions, including calcination temperature and duration, allows for the regulation of surface O/N ratio of TaON particles to unity, resulting in optimized photocatalytic activity. Photoelectrochemical assessment and intensity modulated photocurrent spectroscopy provide convincing evidence for improved charge transfer efficiency of photoexcited holes at TaON surface. A Z-scheme overall water splitting is accomplished by employing the TaON as an effective oxygen evolution photocatalyst, SrTiO3:Rh as a hydrogen evolution photocatalyst, and reduced graphene oxide (rGO) as a solid-state electron mediator. This work presents a promising strategy for the synthesis of high-quality oxynitride materials in application to photocatalytic water splitting.

Synthesis of N/P/S Co-doped porous carbons by carbonizing polyphosphazene microspheres for highly selective adsorption of Pb (II)

Heteroatom-doping has emerged as a promising approach for enhancing the properties of carbon materials, particularly in the treatment of heavy-metal wastewater. However, the simultaneous synthesis of multi-heteroatom co-doped carbon materials poses significant complexity and challenges. Consequently, there is an increasing demand for the development of non-toxic and straightforward methods to prepare such materials. In this study, we present a novel approach for the synthesis of N/P/S co-doped porous carbonaceous adsorbents using polyphosphazene as precursors. Our focus is specifically on their effectiveness in adsorbing Pb (II). The results reveal that the synthesized adsorbents, denoted as carbonized polyphosphazene or CZ-600 exhibited a high carbon content co-doped with N, P and S atoms, as well as an abundance of oxygen-containing functional groups and a porous structure. These characteristics collectively contribute to the exceptional adsorption capacity of CZ-600 for Pb (II), with a maximum adsorption capacity of 121.7 mg/g and an equilibrium time as short as 20 min. Further investigations of the adsorption process involve fitting adsorption isotherm, kinetic, and thermodynamic models, revealing chemical adsorption as the predominant mechanism, supported by contributions from micropore adsorption and electrostatic interactions. This work proposes a sustainable and efficient solution for the treatment heavy-metal wastewater, which not only advances the understanding of heteroatom-doped carbon materials but also provides valuable insights into their practical applications in environmental remediation.

LONESOME HIGHWAY-TARGET OF MONOPTEROS5 transcription factor complex promotes a predifferentiation state for xylem vessel differentiation in the root apical meristem by inducing the expression of VASCULAR-RELATED NAC-DOMAIN genes.

In Arabidopsis thaliana, heterodimers comprising two bHLH family proteins, LONESOME HIGHWAY (LHW) and TARGET OF MONOPTEROS5 (TMO5) or its homolog TMO5-LIKE 1 (T5L1) control vascular development in the root apical meristem (RAM). The LHW-TMO5/T5L1 complex regulates vascular cell proliferation, vascular pattern organization, and xylem vessel differentiation; however, the mechanism of preparation for xylem vessel differentiation in the RAM remains elusive. We examined the relationship between LHW-T5L1 and VASCULAR-RELATED NAC-DOMAIN (VND) genes, which are key regulators of vessel differentiation, using reverse genetics approaches. LHW-T5L1 upregulated the expression of VND1, VND2, VND3, VND6, and VND7 but not that of other VNDs. The expression of VND1-VND3 in the RAM was decreased in lhw. In vnd1 vnd2 vnd3 triple loss-of-function mutant roots, metaxylem differentiation was delayed, and VND6 and VND7 expression was reduced. Furthermore, transcriptome analysis of VND1-overexpressing cells revealed that VND1 upregulates genes involved in the synthesis of secondary cell wall components. These results suggest that LHW-T5L1 upregulates VND1-VND3 at the early stages of vascular development in the RAM, and VNDs promote a predifferentiation state for xylem vessels by triggering low levels of VND6 and VND7 as well as genes for the synthesis of secondary cell wall materials.

Argon Plasma Bombardment Induces Surface‐Rich Sn Vacancy Defects to Enhance the Thermoelectric Performance of Polycrystalline SnSe

AbstractNanoscale defects can induce the effective modulation of carrier concentration, mobility, and phonon scattering to secure high thermoelectric performance in semiconductors. However, it is still limited to effectively controlling nanoscale defects in thermoelectric materials. Here, argon plasma bombardment is employed to introduce a large number of point defects and dislocations in microcrystalline SnSe powders, synthesized by a solvothermal method. After sintering these powders into polycrystalline bulk materials, bulk SnSe shows the ZT increasing by up to 66.7% (from 0.36 to 0.6 at 773 K). Through detailed micro/nanostructure characterizations and first‐principles calculations, the underlying mechanism is elucidated for the evaluation of thermoelectric performance. This work provides a deep understanding of the mechanism of nanoscale defects in modulating thermoelectric performance and presents experimental evidence and experience for the design and synthesis of efficient thermoelectric materials, making significant contributions to future green energy technologies.

Three-dimensional porous polyimide anode for high-rate lithium ion batteries

Polymeric electrode materials are widely used in many applications but still suffer from poor electrical conductivity and slow transport kinetics, especially poor performance at high current densities. Herein, a polyimide electrode structure with 3D-ordered interconnected gradient pores was developed to improve the lithium-ion transport efficiency. The homogeneous mixed PMTA-PMMA composite was prepared by a simple one-pot method, followed by removal of PMMA (polymethyl methacrylate) spherical porogenic agent during the synthesis of polyimide material at high temperatures to form a low curvature gradient-pore structure. The large pores in the electrode enhanced the ion transport ability and improved the electrolyte infiltration rate, while the small pores improved the active specific surface area and guided the deposition of lithium ions. As a result, a high specific capacity reaching 907 mAh/g was maintained even after 1000 cycles at 5 A/g, a value about 3-fold that of un-pored electrode materials. The experimental studies and DFT calculations were used to develop a 24Li storage mechanism of PMTA, and the active electrode material was fully electrochemically activated by the constructed three-dimensional porous electrode structure. Overall, the proposed porous material with a high active area and porosity looks potential for use as an ultra-fast charging and discharging electrode of lithium-ion batteries with high specific capacity and excellent cycling performance.

Modulation of Carbazole/Phenol Resonant Partners within Diboron‐Based Multi‐Resonance Emitters Enable High‐Performance Narrowband Green to Red OLEDs

AbstractDiboron‐based multi‐resonance (MR) molecules featuring para‐B‐π‐B configuration represent a highly promising class of emitters for red and near‐infrared organic light‐emitting diodes (OLEDs). The emission spectra of the diboron‐based MR emitters can be fine‐tuned by modulating the carbazole/phenol resonant partners. However, beyond spectral tuning, a comprehensive understanding of the intricate relationship between molecular structure, and the overall properties of diboron‐based MR emitters remains elusive. In this work, through meticulous molecular design and precise material synthesis, the study has constructed three new MR emitters and completed the establishment of the diboron‐based MR molecular family involving a carbazole/phenol resonant counterpart. These emitters facilitate a systematic investigation into the comprehensive impact of resonant partners on critical properties beyond spectral tuning, such as thermally activated delayed fluorescence, full‐width at half‐maximum, and horizontal orientation ratio. Eventually, by employing these emitters, high‐performance narrowband emitting OLEDs with maximum external quantum efficiencies (EQEmaxs) of 30.2%, 33.0%, and 37.0% are fabricated for the green, yellow, and red devices, respectively, together with exceptional operational lifetimes. In particular, both yellow and red OLEDs exhibit unprecedented low‐efficiency roll‐off, maintaining high EQEs over 30% and 25% at the ultrahigh brightness levels of 10 000 and 100 000 cd m−2, respectively.

Cutting Edge High‐Throughput Synthesis and Characterization Techniques in Combinatorial Materials Science

AbstractThe Materials Genome Initiative is expected to accelerate the materials discovery and design by fundamentally changing the trial‐and‐error research paradigm. However, mass data from high‐throughput experiments is still essential for the revelation of rules and verification of theories. In fact, the development of combinatorial materials science is always on the strength of the upgrade and evolution of high‐throughput techniques in each stage, especially high‐throughput materials synthesis and characterization. Herein, this review summarizes the high‐throughput synthesis methods for combinatorial materials libraries, especially the co‐deposition and masking techniques of thin‐film fabrication; and details the high‐throughput characterization methods for specific material properties and typical material categories, which comes down to the spectroscopy and microscopy techniques. It is considered that high‐throughput concepts will be the predominant lab experimentation in the future, along with advanced experimental techniques and convenient data processing procedures. Before that, more cooperation between multiple researchers from different fields should be conducted to complete the combinatorial materials research, since the high‐throughput technology covers multiple disciplines with a huge span.

2024 Roadmap on Magnetic Microscopy Techniques and Their Applications in Materials Science

Abstract Considering the growing interest in magnetic materials for unconventional computing, data storage, and sensor applications, there is active research not only on material synthesis but also characterisation of their properties. In addition to structural and integral magnetic characterisations, imaging of magnetization patterns, current distributions and magnetic fields at nano- and microscale is of major importance to understand the material responses and qualify them for specific applications. In this roadmap, we aim to cover a broad portfolio of techniques to perform nano- and microscale magnetic imaging using SQUIDs, spin center and Hall effect magnetometries, scanning probe microscopies, x-ray- and electron-based methods as well as magnetooptics and nanoMRI. The roadmap is aimed as a single access point of information for experts in the field as well as the young generation of students outlining prospects of the development of magnetic imaging technologies for the upcoming decade with a focus on physics, materials science, and chemistry of planar, 3D and geometrically curved objects of different material classes including 2D materials, complex oxides, semi-metals, multiferroics, skyrmions, antiferromagnets, frustrated magnets, magnetic molecules/nanoparticles, ionic conductors, superconductors, spintronic and spinorbitronic materials.

Construction of porous flower-like Ru-doped CoNiFe layered double hydroxide for supercapacitors and oxygen evolution reaction catalysts

In recent years, ternary layered double hydroxide (LDH) has become a research hotspot for electrode materials and oxygen evolution reaction (OER) catalyst due to the enhanced synergistic effect between individual elements. However, the application of LDH is greatly limited by its low electrical conductivity and the disadvantage that nanosheets tend to accumulate and mask the active sites. Herein, a novel Ru-doped CoNiFe − LDH was prepared via a facile hydrothermal method. According to the density functional theory (DFT) calculations, the doping of Ru element could improve electron state density and band gaps of LDH and consequently boosted the electrochemical reaction kinetics as well as electrical conductivity. Furthermore, introduction of Ru atom induced the formation of porous flower-like structures in nanosheets. Compared to CoNiFe − LDH (28.9 m2/g), Ru-doped CoNiFe − LDH performed larger specific surface area of 53.1 m2/g, resulting in more electrochemically active sites. In these case, Ru-doped CoNiFe − LDH demonstrated better energy storage performance of 176.0 mAh/g at 1 A/g compared to original CoNiFe − LDH (78.9 mAh/g at 1 A/g). Besides, the assembled Ru-doped CoNiFe − LDH//activated carbon (AC) device delivered a maximum energy density of 36.4 W h kg−1 at the power density of 740.3 W kg−1 and an outstanding cycle life (78.7 % after 10,000 cycles). Meanwhile, Ru-doped CoNiFe − LDH exhibited lower overpotential (339 mV at 50 mA cm−2) and Tafel slope (93.2 mV dec−1). Therefore, this work provided novel and valuable insights into the rational doping of Ru elements for the controlled synthesis of supercapacitor electrode materials and OER catalysts.

Rapid mechanochemical synthesis of high-performance Na4Fe2.94Al0.04(PO4)2(P2O7)/C cathode material for sodium-ion storage

Na4Fe3(PO4)2(P2O7) is regarded as a promising cathode material for sodium-ion batteries due to its affordability, non-toxic nature, and excellent structural stability. However, its electrochemical performance is hampered by its poor electronic conductivity. Meanwhile, most of the previous studies utilized spray-drying and sol–gel methods to synthesize Na4Fe3(PO4)2(P2O7), and the large-scale synthesis of the cathode material is still challenging. This study presents a composite cathode material, Na4Fe2.94Al0.04(PO4)2(P2O7)/C, prepared via a straightforward ball-milling technique. By substituting Al3+ minimally into the Fe2+ site of NFPP, Fe defects are introduced into the structure, hindering the formation of NaFePO4 and thereby enhancing Na-ion diffusion kinetics and conductivity. Additionally, the average length of AlO bonds (2.18 Å) is slightly smaller than that of FeO bonds (2.19 Å), contributing to the superior structural stability. The smaller ionic radii of Al3+ induce lattice contraction, further enhancing the structural stability. Moreover, the surface of material particles is coated with a thin layer of carbon, ensuring excellent electrical conductivity and outstanding structure stability. As a result, the Na4Fe2.94Al0.04(PO4)2(P2O7)/C cathode exhibits excellent electrochemical performance, leading to high discharge capacity (128.1 mAh g−1 at 0.2 C), outstanding rate performance (98.1 mAh g−1 at 10 C), and long cycle stability (83.7 % capacity retention after 3000 cycles at 10 C). This study demonstrates a low-cost, ultra-stable, and high-rate cathode material prepared by simple mechanical activation for sodium-ion batteries which has application prospects for large-scale production.

Synergizing experimental and theoretical insights: Unveiling the solar potential of La2NiMnO6 double perovskite for enhanced efficiency and sustainability in photovoltaics

Amidst the escalating demand for sustainable energy solutions, this research delves into the competence of double perovskite oxide La2NiMnO6 as a solar cell luminary. Addressing material synthesis, structural intricacies, and device construction, the study responds to the limitations of labour-intensive first-generation Si solar cells along with the toxicity of lead attributed perovskite solar cells, steering towards a revolutionary era. La2NiMnO6 distinctive attributes a formidable dielectric constant, positioning it as a beacon in solar energy. Crafted via sol gel citrate alchemy, its structural, optical, and electronic intricacies were meticulously explored. Experimental insights into the fabrication process, employing optimised spray pyrolysis layers, enrich the narrative. Structural analyses confirm La2NiMnO6 prowess, while optical studies unveil its visible spectrum absorbance. Simulations and the experimental J-V curve show PCEs of 10% and 4.5 %, solidifying the La2NiMnO6 stance in the all-inorganic perovskite solar cell realm. This study propels the evolution of photovoltaic technology, laying pathways for sustainable energy alternatives and setting new benchmarks.