Design Of Multifunctional Materials Research Articles

Superconductivity in Diamond-Like BC15.

Advancing the compositional space of a compound class can result in intriguing superconductors, such as LaH10. Herein, we performed a comprehensive first-principles structural search on a binary B-C system with various chemical compositions. The identified diamond-like BC15, named d-BC15, is thermodynamically superior to the synthesized BC3 and BC5. Interestingly, d-BC15 shows anisotropic superconductivity resulting from three distinct Fermi surfaces. Its predicted critical temperature (Tc) is 43.6 K at ambient pressure, beyond the McMillan limit. d-BC15 reaches a maximum of around 75 K at 0.43% hole doping due to the substantially enhanced density of states at the Fermi level. Additionally, d-BC15 demonstrates superhard characteristics with a Vickers hardness of 75 GPa. The calculated tensile and shear stresses are 72 and 73 GPa, respectively. The combination of high superconductivity and superhardness in d-BC15 offers new insights into the design of multifunctional materials.

Unprecedented mechanical wave energy absorption observed in multifunctional bioinspired architected metamaterials

In practical engineering, noise and impact hazards are pervasive, indicating the pressing demand for materials that can absorb both sound and stress wave energy simultaneously. However, the rational design of such multifunctional materials remains a challenge. Herein, inspired by cuttlebone, we present bioinspired architected metamaterials with unprecedented sound-absorbing and mechanical properties engineered via a weakly-coupled design. The acoustic elements feature heterogeneous multilayered resonators, whereas the mechanical responses are based on asymmetric cambered cell walls. These metamaterials experimentally demonstrated an average absorption coefficient of 0.80 from 1.0 to 6.0 kHz, with 77% of the data points exceeding the desired 0.75 threshold, all with a compact 21 mm thickness. An absorptance-thickness map is devised for assessing the sound-absorption efficiency. The high-fidelity microstructure-based model reveals the air friction damping mechanism, with broadband behavior attributed to multimodal hybrid resonance. Empowered by the cambered design of cell walls, metamaterials shift catastrophic failure toward a progressive deformation mode characterized by stable stress plateaus and ultrahigh specific energy absorption of 50.7 J/g—a 558.4% increase over the straight-wall design. After the deformation mechanisms are elucidated, a comprehensive research framework for burgeoning acousto-mechanical metamaterials is proposed. Overall, our study broadens the horizon for multifunctional material design.

Spatial segregation of catalytic sites within Pd doped H-ZSM-5 for fatty acid hydrodeoxygenation to alkanes

Spatial control over features within multifunctional catalysts can unlock efficient one-pot cascade reactions, which are themselves a pathway to aviation biofuels via hydrodeoxygenation. A synthesis strategy that encompasses spatial orthogonality, i.e., one in which different catalytic species are deposited exclusively within discrete locations of a support architecture, is one solution that permits control over potential interactions between different sites and the cascade process. Here, we report a Pd doped hierarchical zeolite, in which Pd nanoparticles are selectively deposited within the mesopores, while acidity is retained solely within the micropores of ZSM-5. This spatial segregation facilitates hydrodeoxygenation while suppressing undesirable decarboxylation and decarbonation, yielding significant enhancements in activity (30.6 vs 3.6 moldodecane molPd−1 h−1) and selectivity (C12:C11 5.2 vs 1.9) relative to a conventionally prepared counterpart (via wet impregnation). Herein, multifunctional material design can realise efficient fatty acid hydrodeoxygenation, thus advancing the field and inspiring future developments in rationalised catalyst design.

SiC skeleton‐reinforced highly oriented graphite with good thermophysical and electromagnetic shielding properties

AbstractThe design of multifunctional materials with good thermophysical and electromagnetic shielding properties is desirable to overcome overheating and electromagnetic interference (EMI) in electronic devices. In this study, three‐dimensional (3D) continuous SiC skeleton‐reinforced highly oriented graphite flake (GF@SiC) composites were fabricated by combining molten salt synthesis, heat treatment, and spark plasma sintering. When the SiC content was higher than 9 vol.%, a 3D continuous SiC skeleton was formed, which effectively constrained the cross‐plane thermal expansion of the GF@SiC composites. Highly oriented GFs endowed the composites with good thermal conductivity (TC) along the basal plane and effective EMI shielding in the X‐band. The composites with SiC concentrations of 9 vol.% exhibited an optimal comprehensive performance with a high TC of 322 W/m/K in the basal plane direction, a low thermal expansion value of 10.5 × 10−6/K in the through‐plane direction, and EMI shielding effectiveness of 36 dB. Our strategy provides a promising and practical approach for realizing graphite‐based composites to meet the current demands for electronic devices.

Accelerating metal nanoparticle exsolution by exploiting tolerance factor of perovskite stannate.

The octahedral symmetry in ionic crystals can play a critical role in atomic nucleation and migration during solid-solid phase transformation. Similarly, octahedron distortion, which is characterized by Goldschmidt tolerance factor, strongly influences the exsolution kinetics in the perovskite lattice framework during high-temperature annealing. However, a fundamental study on manipulating the exsolution process by octahedron distortion is still lacking. In this study, we accelerate Ni metal exsolution on the surface of perovskite stannates by increasing the [BO6] octahedron distortion in the lattices. Decreasing the A-site ionic radius (rBa2+ = 161 pm → rSr2+ = 144 pm → rCa2+ = 134 pm) increased the density of exsolved Ni nanoparticles by up to 640% (i.e., 47 particles μm-2 of Ba(Sn, Ni)O3 → 304 particles μm-2 of Ca(Sn, Ni)O3) after the identical exsolution process. Based on the theoretical calculation and experimental characterization, the decrease in crystal symmetry by octahedral distortion promoted the Ni exsolution owing to the boosted Ni migration by weakening the bond strength and generating domain boundaries. The findings highlight the importance of octahedral distortion to control atomic migration through the perovskite lattice framework and provide a strategy to tailor the density of uniformly populated nanoparticles in nanocomposite oxides for multifunctional material design.

Detection and elimination of tetracycline: Constructing multi-mode carbon dots for ultra-sensitive visual assay and CDs/TiO2 for photocatalytic degradation

Ultrasensitive detection and degradation of tetracycline (TC) has gained increasing attention owing to their inevitable detriments to human and ecosystem. Many studies have focused on mono-functional detection or degradation. However, the design of multi-functional materials is still a challenge. Till now, a novel protocol applied to the consecutive detection and complete degradation of TC are rarely successfully reported. Herein, we not only developed a multi-mode optical carbon dots (CDs) for ultra-sensitive sensing, but also further manufactured CDs/TiO2 photocatalyst that can degrade TC 100 %, completely eliminating the TC for the first time. The as-prepared CDs can selectively detect TC with low detection limit of 5.2 nM and 10.7 nM within only 40 s, accompanied by wide linear interval of 1.0–50.0 μM and 50.0–250.0 μM, respectively. Therefore, the fabricated point-of-care testing platform can realize “in-situ” visual detection rapidly and efficiently. Furthermore, a highly active CDs/TiO2 photocatalyst was prepared by rationally modifying CDs on TiO2 and exhibited almost 100 % degradation behavior towards TC within 70 min. The mechanism of fluorescence quenching and photocatalysis were lucubrated. Notably, our proposed protocol can drive consecutive detection and elimination towards tetracycline, which powerfully reduces the potential harm and provides a new strategy for the eradication of pollutants.

The weaving art of mechanically and electronically robust hydrogel realizes multi-dimensional response of stretchable sensors

In recent years, hydrogel-based soft electronics have been developed for the application of human motion, flexible robots and foldable displays. However, most existing conductive hydrogels have low toughness, single electron conduction or ionic conduction and poor adaptability towards complex applications. In this work, we obtained the toughness fiber-like hydrogel in three steps by doping nanofillers, directional extrusion freezing, and salting out. The proposed tough fiber-like hydrogel has a rich porous structure, which is achieved by doping the hydrophilic graphene nanosheets (HGNs) into a physically cross-linking polyvinyl alcohol (PVA) gel matrix. Directional extrusion freezing and salting out effect endow fiber-like hydrogel with better orientation ultimate nominal stress (∼9.5 MPa) and nominal strain (∼2200%). Meanwhile, the abundant porous structure facilitates ion migration and greatly enhances the ionic conductivity (up to 2.8 S m −1, at f = 1 MHz) of the hydrogel. The presence of HGNs endows the fiber-like hydrogel with excellent electronic conduction properties. Moreover, the weaving strategy is proposed to fabricate fiber-like hydrogel into hydrogel fabric film, which is effective for increased safety of stress-induced deformation and crack propagation. The woven hydrogel mesh bag can lift 6 kg of watermelon and the woven hydrogel net can bear a top-down weight impact of 1 kg. We also develop a novel type of woven hydrogel glove that can monitor complex hand movement. This work will provide new insight into the design of multifunctional materials with applications on electronic skin, wearable devices, and health monitoring.

Structural Design Induced Electronic Optimization in Single-Phase MoCoP Nanocrystal for Boosting Oxygen Reduction, Oxygen Evolution, and Hydrogen Evolution.

Structural and compositional design of multifunctional materials is critical for electrocatalysis, but their rational modulation and effective synthesis remain a challenge. Herein, a controllable one-pot synthesis for construction of trifunctional sites and preparation of porous structures is adopted for synthesizing dispersed MoCoP sites on N, P codoped carbonized substance. This tunable synthetic strategy also endorses the exploration of the electrochemical activities of Mo (Co)-based unitary, Mo/Co-based dual and MoCo-based binary metallic sites. Eventually benefiting from the structural regulation, MoCoP-NPC shows excellent oxygen reduction abilities with a half-wave potential of 0.880V, and outstanding oxygen evolution and hydrogen evolution performance with an overpotential of 316mV and 91mV, respectively. MoCoP-NPC-based Zn-air battery achieves excellent cycle stability for 300h and a high open-circuit voltage of 1.50V. When assembled in a water-splitting device, MoCoP-NPC reaches 10mA cm-2 at 1.65V. Theoretical calculations demonstrate that the Co atom in the single-phase MoCoP has a low energy barrier for oxygen evolution reaction (OER) owing to the migration of Co 3d orbital toward the Fermi level. This work shows a simplified method for controllable preparation of prominent trifunctional catalysts.

Design Strategy for Enabling Multifunctional Properties of Anthracene-based Emitters.

The design of multifunctional materials is a challenging and important objective for a wide array of multidisciplinary applications. However, a multifunctional organic emitter exhibiting simultaneous aggregation-induced emission (AIE), multi-responsive polymorphs, mechanoluminescence and electroluminescence have been scarce. In this study, two anthracene based compounds, namely 10-(4-(9H-carbazol-9-yl)phenyl)anthracene-9-carbonitrile (CzPACN) and 10-(4-(di-p-tolylamino)phenyl)anthracene-9-carbonitrile (DTPACN) was designed and synthesized with rigid and flexible donors, respectively. The CzPACN shows the bright blue emission and DTPACN shows the bright green emission in solution. We have demonstrated an effective strategy to achieve three polymorphic phases such as DTPACN-α, DTPACN-β and DTPACN-γ from DTPACN by controlling the temperature. Under mechanical stimuli, highly restricted and non-planar crystals of the structurally tuned polymorphs DTPACN-α, and DTPACN-β exhibited red shifted emission and DTPACN-γ showed blue shifted emission. Conversely, CzPACN is not showing polymorphism and is not sensitive to external stimuli. In addition, blue and green OLEDs were fabricated using CzPACN and DTPACN, respectively, as an emitter and achieved a maximum external quantum efficiency (EQEmax ) of 5.5% and 5.7%, respectively, for blue and green OLEDs. Further, this study suggests designing multi-responsive smart materials via a simple modification by introducing a non-planar unit with a large twist.

Imatinib cation based MOIFs with [Fe(CN)5NO]2−, [Fe(CN)6]3− [Fe(CN)6]4− as adsorbent of organic pollutants, and their protein interaction study

Inorganic-organic hybrid (IOH) compounds are being widely used in the design of multifunctional materials owing to their rich properties and flexible assembly. Here, we report three metal organic ionic frameworks (MOIFs)/ IOH, for the adsorption of toxic organic pollutants and Bovine Serum Albumin (BSA) interaction, synthesized via simple ion-exchange mechanism in water using Na2[Fe(CN)5NO], K3[Fe(CN)6], K4[Fe(CN)6] and 4-[(4-methylpiperazin-1-yl)methyl]-N-(4-methyl-3-{[4-(pyridin-3-yl)pyrimidin-2yl]amino}phenyl) mesylate (ImM). These were characterized through powder XRD, NMR, UV/ Vis and FTIR techniques for their structural elucidation. The thermal gravimetric analysis (TGA) revealed their two transitions due to loss of water and organic compound. Additionally, the band gap was found in the range of 3.2 to 3.3 eV, inferred their applicability in the field of semiconductors. MOIFs have shown the adsorption of toxic pollutants (Organic dyes) investigated through thermal kinetics and activation parameters which inferred about the interaction between organic dyes and MOIFs as characteristics for the adsorption system. Adsorption has also been analyzed through conductivity data where according to Ostwald's dilution law for weak electrolytes was applied. For knowing medicinal aspects, MOIFs have also been tested for BSA binding activity analyzed with UV–Vis, fluorescence and docking studies, which showed good quenching efficacy as well as interaction ability.

Alkyl-substituted bipyridyl platinum (II) complexes bearing alkynyl-naphthalimide ligands: Synthesis, photophysical properties, and tunable aggregation-induced emission activity

Different alkyl chains were introduced into alkynyl-naphthalimide ligands and bipyridine ligands to synthesize five platinum complexes, their structures were characterized and the photophysical properties were systematically investigated. It was found that the introduction of alkyl chains had no obvious effect on the absorption and emission of these complexes in dilute solution, while influence aggregation-induced emission activity in aggregated state. In the mixed solvent system of tetrahydrofuran and ethylene glycol, the shorter alkyl chains on the bipyridine ligands strengthen the aggregation-induced phosphorescence emission (AIPE) properties of complexes, however, the introduction of different alkyl chains on the alkynyl-naphthalimide ligands makes no difference on their AIPE properties. Combining the single crystal results and Hirshfled surface analysis, the photophysical properties of these complexes in aggregated state were affected by the stacking modes, which is due to the different interactions. This research may broaden the scope for the design of multi-functional materials adopting different aggregation states.

Discontinuous Tension-Controlled Transition between Collective Actuations in Active Solids.

The recent finding of collective actuation in active solids-solids embedded with active units-is a new promise for the design of multifunctional materials with genuine autonomy, and a better understanding of dense biological systems. Here, we combine the experimental study of centimetric model active solids, the numerical study of an agent-based model, and theoretical arguments to reveal a new form of collective actuation and how mechanical tension can serve as a general mechanism for transitioning between different collective actuation regimes. The presence of hysteresis when varying tension back and forth highlights the nontrivial selectivity of collective actuations.

Aggregation Effect on Multiperformance Improvement in Aryl-Armed Phenazine-Based Emitters.

The concept of aggregate science was proposed to explain changes in materials performance that accompany the generation of aggregates, but aggregation-triggered multifunction improvements in a class of materials have rarely been reported. Herein, we present the first report of a new class of multifunctional aggregation-induced emission (AIE) luminogens (AIEgens) based on 5,10-diarylphenazine (DPZ) derivates with full-wavelength emission. Intriguingly, multiple properties, such as fluorescence intensity and free radical and type I reactive oxygen species (ROS) efficiencies, could be simultaneously activated from the unimolecular level to the aggregate state. The mechanisms of this multiple performance improvement are discussed in detail based on sufficient performance characterization, and some of the newly prepared AIEgens exhibited toxicity to cancer cells during photodynamic therapy. This work systematically demonstrates the positive effect of aggregation on improving multiple functions of materials, which is expected to promote the development of aggregate science theory for the design of multifunctional materials.

Circularly polarized luminescence in the one-dimensional assembly of binaphtyl-based Yb(iii) single-molecule magnets.

Lanthanide ions have attracted great interest owing to their optical and magnetic properties. Single-molecule magnet (SMM) behavior has been a fascinating science for thirty years. Moreover, chiral lanthanide complexes allow the observation of remarkable circularly polarized luminescence (CPL). However, the combination of both SMM and CPL behaviors in a single molecular system is very rare and deserves attention in the design of multifunctional materials. Four chiral one-dimensional coordination compounds involving 1,1'-Bi-2-naphtol (BINOL)-derived bisphosphate ligands and the Yb(iii) centre were synthesized and characterized by powder and single-crystal X-ray diffraction. All the Yb(iii)-based polymers displayed field-induced SMM behavior with magnetic relaxation occurring by applying Raman processes and near infrared CPL in the solid state.

Multifunctional materials for catalyst-specific heating and thermometry in tandem catalysis.

A multifunctional material design, integrating catalytic as well as auxiliary magnetic susception and contactless thermal sensing functionalities, unlocks catalyst-specific heating and thermometry for spatially proximate solid catalysts in a single reactor. The new concept alleviates temperature incompatibilities in tandem catalysis, as showcased for the direct production of propene from ethene, via sequential olefin dimerization and metathesis reactions.

Sulfur Vacancy-Rich CuS for Improved Surface-Enhanced Raman Spectroscopy and Full-Spectrum Photocatalysis.

There are growing interests in the development of bifunctional semiconducting nanostructures for photocatalysis and real-time monitoring of degradation process on catalysts. Defect engineering is a low-cost approach to manipulating the properties of semiconductors. Herein, we prepared CuS nanoplates by a hydrothermal method at increasing amounts of thioacetamide (CS-1, CS-2, and CS-3) and investigated the influence of sulfur vacancy (Vs) on surface-enhanced Raman spectroscopy (SERS) and photocatalysis performance. SERS intensity of 4-nitrobenzenethiol on CS-3 is 346 and 17 times that of CS-1 and CS-2, respectively, and enhancement factor is 1.34 × 104. Moreover, SERS is successfully applied to monitor the photodegradation of methyl orange. In addition, CS-3 also exhibited higher efficiency of Cr(VI) photoreduction than CS-1 and CS-2, and removal rate is 88%, 96%, and 73% under 2 h UV, 4 h visible, and 4 h near-infrared illumination, respectively. A systematic study including electron paramagnetic resonance spectra, photoelectrochemical measurements, and nitrogen adsorption isotherms were conducted to investigate the underlying mechanism. This work may help to understand the impact of vacancy defect on SERS and photocatalysis, and provide an effective and low-cost approach for the design of multifunctional materials.

Fully Automated Optimization of Robot‐Based MOF Thin Film Growth via Machine Learning Approaches

AbstractMetal–organic frameworks (MOFs), have emerged as ideal class of materials for the identification of structure–property relationships and for the targeted design of multifunctional materials for diverse applications. While the powder form is most common, for the integration of MOFs into devices, typically thin films of surface anchored MOFs (SURMOFs), are required. Although the quality of SURMOFs emerging from layer‐by‐layer approaches is impressive, previous works revealed that the optimum growth conditions are very different between different types of MOFs and different substrates. Furthermore, the choice of appropriate synthesis conditions (e.g., solvents, modulators, concentrations, immersion times) is crucial for the growth process and needs to be adjusted for different substrates. Machine learning (ML) approaches show great promise for multi‐parameter optimization problems such as the above discussed growth conditions for SURMOF on a particular substrate. Here, this work presents an ML‐based approach allowing to quickly identify optimized growth conditions for HKUST‐I SURMOFs with high crystallinity and uniform orientation. This process can subsequently be used to optimize growth on other types of substrates. In addition, an analysis of the results allows to gain further insights into the factors governing the growth of MOF thin films.

Multifunctional material design for strain sensing: Carbon black effect on mechanical and electrical properties of polyamides

This work investigates the coupled effect on mechanical and electrical properties of carbon black dispersed in polyamide 6 and 6.6 matrices. The CB content is varied between 15 % and 25 % wt. The elastic modulus increases of 12 % by increasing the CB concentration. Results reveal the capability of CB to functionalize thermoplastic polymers by activating conductive networks, as obtained over the percolation threshold of 13 % wt. The conductivity sensitivity to the mechanical strain is analyzed within direct (DC) and alternate current (AC) in the range of 0–100 kHz. Composite with lower CB concentrations exhibited a linear increase of the Gauge Factor (GF) with the frequency (from 2 to 4 at 20 %wt), while at 25 % wt of CB, the GF is 17 in DC regime and linearly decreases toward 6, at 100 kHz. A novel model for the estimation of the material Gauge Factor (GF) variation with the applied electric frequency is proposed.

Searching guidelines for scalable and controllable design of multifunctional materials and hybrid interfaces: Status and perspective

The urgent need to address the global sustainability issues that modern society is currently facing requires the development of micro and nanotechnologies, which rely largely on functional materials. Beyond studies focused solely on low-dimensional materials, broader research related to multifunctionality has shown that the major efforts to meet these criteria for new electronic, photonic, and optoelectronic concepts, particularly to achieve high-performance devices, are still challenging. By exploiting their unique properties, a comprehensive understanding of the implications of research for the synthesis and discovery of novel materials is obtained. The present article encompasses innovation research as an alternative optimization and design for sustainable energy development, bridging the scaling gap in atomically controlled growth in terms of surface heterogeneity and interfacial engineering. In addition, the corresponding research topics are widely regarded as a scientometric analysis and visualization for the evaluation of scientific contributions into the early 20 years of the 21st century. In this perspective, a brief overview of the global trends and current challenges toward high-throughput fabrication followed by a scenario-based future for hybrid integration and emerging structural standards of scalable control design and growth profiles are emphasized. Finally, these opportunities are unprecedented to overcome current limitations, creating numerous combinations and triggering new functionalities and unparalleled properties for disruptive innovations of Frontier technologies.

Electronically regulated FeOOH/c-NiMoO4 with hierarchical sandwich structure as efficient electrode for oxygen evolution and hybrid supercapacitors

Electronic regulation via interface engineering is an effective strategy to promote electrochemical performances of nanomaterials. This work reported a facile method to prepare sandwich-like FeOOH/c-NiMoO4 with FeOOH as the mid-layer and the composite of NiMoO4-Ni(OH)2 nanosheets on both sides of FeOOH. Benefiting from the novel hierarchical porous structures and compositional features, the obtained FeOOH/c-NiMoO4 showed excellent electrochemical performances as electrodes for oxygen evolution reaction (OER) and hybrid supercapacitors (HSCs). It demonstrates excellent OER performances with an overpotential of 254 mV to reach the current density of 10 mA cm−2, a Tafel slope of 58 mV dec−1, and a low applied potential difference of 1.51 V at 10 mA cm−2 for overall water splitting and yields a high specific capacity of 1137 C g−1 (specific capacitance of 2273 F g−1) at 1 A g−1 for SCs in an alkaline electrolyte. First-principle calculations were employed to explore the origin. This work manifests the feasibility of rational design of multi-functional materials via electronic modulation for overall water splitting and energy-storage devices.