Aldol Condensation for the Construction of Organic Functional Materials.

Aldol condensation is a cost-effective and sustainable synthetic method, offering the advantages of low complexity, substrate universality, and high efficiency. Over the past decade, it has become popular for creating next-generation organic functional materials, particularly rigid-rod conjugated (semi)conductors. This review focuses on conjugated small molecules, oligomers, and polymeric (semi)conductors synthesized through aldol condensation, with emphasis on their remarkable features in advancing n-type organic field-effect transistors (OFETs), organic electrochemical transistors (OECTs), organic photovoltaics (OPVs), and organic thermoelectrics (OTEs) as well as NIR-II photothermal conversion. Coherence character, optical properties, microstructure, and chain conformation are investigated to understand material-property relationships. Future applications and challenges in this area are also discussed.

Versatile Neuromorphic Modulation and Biosensing based on N-type Small-molecule Organic Mixed Ionic-Electronic Conductors.

The ion/chemical-based modulation feature of organic mixed ionic-electronic conductors (OMIECs) are critical to advancing next generation bio-integrated neuromorphic hardware. Despite achievements with polymeric OMIECs in organic electrochemical neuronal synapse (OENS). However, small molecule OMIECs based OENS has not yet been realized. Here, for the first time, we demonstrate an effective materials design concept of combining n-type fused all-acceptor small molecule OMIECs with subtle side chain optimization that enables robustly and flexibly modulating versatile synaptic behavior and sensing neurotransmitter in solid or aqueous electrolyte, operating in accumulation modes. By judicious tuning the ending side chains, the linear oligoether and butyl chain derivative gNR-Bu exhibits higher recognition accuracy for a model artificial neural network (ANN) simulation, higher steady conductance states and more outstanding ambient stability, which is superior to the state-of-art n-type OMIECs based OENS. These superior artificial synapse characteristics of gNR-Bu can be attributed to its higher crystallinity with stronger ion bonding capacities. More impressively, we unprecedentedly realized n-type small-molecule OMIECs based OENS as a neuromorphic biosensor enabling to respond synaptic communication signals of dopamine even at sub-µM level in aqueous electrolyte. This work may open a new path of small-molecule ion-electron conductors for next-generation ANN and bioelectronics.

Emulsion-templated porous polymers: drying condition-dependent properties.

Macroporous materials templated using high internal phase emulsions (HIPEs) are promising for various applications. To date, new strategies to create emulsion-templated porous materials and to tune their properties (especially wetting properties) are still highly required. Here, we report the fabrication of macroporous polymers from oil-in-water HIPEs, bereft of conventional monomers and crosslinking monomers, by simultaneous ring-opening polymerization and interface-catalyzed condensation, without heating or removal of oxygen. The resulting macroporous polymers showed drying condition-dependent wetting properties (e.g., hydrophilicity-oleophilicity from freezing drying, hydrophilicity-oleophobicity from vacuum drying, and amphiphobicity from heat drying), densities (from 0.019 to 0.350 g cc-1), and compressive properties. Hydrophilic-oleophilic and amphiphobic porous polymers turned hydrophilic-oleophobic simply by heating and protonation, respectively. The hydrophilic-oleophobic porous polymers could remove a small amount of water from oil-water mixtures (including surfactant-stabilized water-in-oil emulsions) by selective absorption and could remove water-soluble dyes from oil-water mixtures. Moreover, the transition in wetting properties enabled the removal of water and dyes in a controlled manner. The feature that combines simply preparation, tunable wetting properties and densities, robust compression, high absorption capacity (rate) and controllable absorption makes the porous polymers to be excellent candidates for the removal of water and water-soluble dyes from oil-water mixtures.

Influence of Co2+ Ions on the Microstructure and Mechanical Properties of Ni-W/Diamond Nano-Composite Coatings.

The Co were incorporated into the Ni-W/diamond nano-composite coatings by introducing CoSO4 in the aforesaid plating bath. The effects of the Co content in the electrodeposit on microstructure and mechanical properties were analyzed. The morphology and the composition of the deposits were investigated by means of SEM and EDS, respectively. The Co content in the coatings increases progressively upon increasing the amount of CoSO4 in the plating bath. The addition of small amount of CoSO4 in the plating bath tends to enhance the hardness and wear performance of the Ni-W/diamond nano-composite coatings. While the amount of CoSO4 beyond 0.2 g/L in the plating bath, the hardness and the wear resistance of the coatings decrease sharply.

Effect of Sodium Dodecyl Sulphate and Sodium Bromide Additives on Ni­W Nanocoatings.

Nickel-tungsten (Ni­W) coatings were fabricated by electrodeposition method with varying quantities of sodium dodecyl sulphate and sodium bromide to examine the effects of the aforesaid additives on the coatings. The obtained nanocoatings were studied by X-ray diffraction, scanning electron microscopy, energy dispersive X-ray spectroscopy, and hardness tester. The hardness, tungsten content and grain size attained a maximum value at current density of 0.15 A/cm²,0.1 A/cm² and 0.1 A/cm², respectively. There was a pronounced impact of both the additives on the microstructure and morphology of the coatings. According to results, there are considerable difference in terms of the impact caused by the additives to the tungsten content, hardness and grain size of the coatings. The obtained results suggest that hardness of coatings is mainly contributed by W content in the deposits.

Revisiting the glass transition and dynamics of supercooled benzene by calorimetric studies.

The glass transition and dynamics of benzene are studied in binary mixtures of benzene with five glass forming liquids, which can be divided into three groups: (a) o-terphenyl and m-xylene, (b) N-butyl methacrylate, and (c) N,N-dimethylpropionamide and N,N-diethylformamide to represent the weak, moderate, and strong interactions with benzene. The enthalpies of mixing, ΔH(mix), for the benzene mixtures are measured to show positive or negative signs, with which the validity of the extrapolations of the glass transition temperature T(g) to the benzene-rich regions is examined. The extrapolations for the T(g) data in the mixtures are found to converge around the point of 142 K, producing T(g) of pure benzene. The fragility m of benzene is also evaluated by extrapolating the results of the mixtures, and a fragility m ∼ 80 is yielded. The obtained T(g) and m values for benzene allow for the construction of the activation plot in the deeply supercooled region. The poor glass formability of benzene is found to result from the high melting point, which in turn leads to low viscosity in the supercooled liquid.

Secondary relaxation dynamics in rigid glass-forming molecular liquids with related structures.

The dielectric relaxation in three glass-forming molecular liquids, 1-methylindole (1MID), 5H-5-Methyl-6,7-dihydrocyclopentapyrazine (MDCP), and Quinaldine (QN) is studied focusing on the secondary relaxation and its relation to the structural α-relaxation. All three glass-formers are rigid and more or less planar molecules with related chemical structures but have dipoles of different strengths at different locations. A strong and fast secondary relaxation is detected in the dielectric spectra of 1MID, while no resolved ß-relaxation is observed in MDCP and QN. If the observed secondary relaxation in 1MID is identified with the Johari-Goldstein (JG) ß-relaxation, then apparently the relation between the α- and ß-relaxation frequencies of 1MID is not in accord with the Coupling Model (CM). The possibility of the violation of the prediction in 1MID as due to either the formation of hydrogen-bond induced clusters or the involvement of intramolecular degree of freedom is ruled out. The violation is explained by the secondary relaxation originating from the in-plane rotation of the dipole located on the plane of the rigid molecule, contributing to dielectric loss at higher frequencies and more intense than the JG ß-relaxation generated by the out-of-plane rotation. MDCP has smaller dipole moment located in the plane of the molecule; however, presence of the change of curvature of dielectric loss, ε″(f), at some frequency on the high-frequency flank of the α-relaxation reveals the JG ß-relaxation in MDCP and which is in accord with the CM prediction. QN has as large an in-plane dipole moment as 1MID, and the absence of the resolved secondary relaxation is explained by the smaller coupling parameter than the latter in the framework of the CM.

Anomaly in dielectric relaxation dispersion of glass-forming alkoxy alcohols.

The dielectric relaxations in six primary and secondary alkoxy alcohols with varying molecular size and different separation between -O- and hydroxyl group are studied at temperatures around glass transition. The analyses of the apparent full width at half maximum of the main relaxations of the alkoxy alcohols reveal minima in the temperature dependence of the relaxation dispersions. The stretching exponents for the main relaxations of the alkoxy alcohols are also found not to follow the empirical correlations with other dynamic quantities established for generic liquids. A comparison of the relaxation dispersions in the alkoxy alcohols with those in Debye and non-Debye (generic) liquids is presented. The impacts of the ß-relaxations on the apparent main relaxation widths are reviewed for molecular glass formers.

Unique lead adsorption behavior of activated hydroxyl group in two-dimensional titanium carbide.

The functional groups and site interactions on the surfaces of two-dimensional (2D) layered titanium carbide can be tailored to attain some extraordinary physical properties. Herein a 2D alk-MXene (Ti3C2(OH/ONa)(x)F(2-x)) material, prepared by chemical exfoliation followed by alkalization intercalation, exhibits preferential Pb(II) sorption behavior when competing cations (Ca(II)/Mg(II)) coexisted at high levels. Kinetic tests show that the sorption equilibrium is achieved in as short a time as 120 s. Attractively, the alk-MXene presents efficient Pb(II) uptake performance with the applied sorption capacities of 4500 kg water per alk-MXene, and the effluent Pb(II) contents are below the drinking water standard recommended by the World Health Organization (10 µg/L). Experimental and computational studies suggest that the sorption behavior is related to the hydroxyl groups in activated Ti sites, where Pb(II) ion exchange is facilitated by the formation of a hexagonal potential trap.

Calorimetric determination of fragility in glass forming liquids: T(f) vs. T(g-onset) methods.

The calorimetric determination of the fragility m-index is compared using the T f and T g-onset methods for typical metallic and molecular glass forming systems of Pd39Ni10Cu30P21, glycerol, triacetin and propylene carbonate. The results are evaluated by referring to the standard m-values determined from the kinetic measurements of the viscosity or structural relaxation time in the supercooled liquid regimes. The m-indexes derived from the T f method are found to generally agree well with the kinetic measurements for all the systems. However, a large deviation is shown between the m-indexes calculated with the T g-onset method and the kinetic results for the fragile liquids of triacetin and propylene carbonate, indicating the calorimetric determination of the fragility m-indexes in terms of the T f method produces less uncertainty.

Glass transition and mixing thermodynamics of a binary eutectic system.

A quantitative evaluation of the contribution of mixing thermodynamics to glass transition is performed for a binary eutectic benzil and m-nitroaniline system. The microcalorimetric measurements of the enthalpy of mixing give small and positive values, typically ~200 J mol(-1) for the equimolar mixture. The composition dependence of the glass transition temperature, T(g), is found to show a large and negative deviation from the ideal mixing rule. The Gordon-Taylor and Couchman-Karasz models are subsequently applied to interpret the T(g) behavior, however, only a small fraction of the deviation is explained. The analyses of the experimental results manifest quantitatively the importance of the mixing thermodynamics in the glass transition in miscible systems.

Microscopic dynamics perspective on the relationship between Poisson's ratio and ductility of metallic glasses.

In metallic glasses a clear correlation had been established between plasticity or ductility with the Poisson's ratio νPoisson and alternatively the ratio of the elastic bulk modulus to the shear modulus, K/G. Such a correlation between these two macroscopic mechanical properties is intriguing and is challenging to explain from the dynamics on a microscopic level. A recent experimental study has found a connection of ductility to the secondary ß-relaxation in metallic glasses. The strain rate and temperature dependencies of the ductile-brittle transition are similar to the reciprocal of the secondary ß-relaxation time, τß. Moreover, metallic glass is more ductile if the relaxation strength of the ß-relaxation is larger and τß is shorter. The findings indicate the ß-relaxation is related to and instrumental for ductility. On the other hand, K/G or νPoisson is related to the effective Debye-Waller factor (i.e., the non-ergodicity parameter), f0, characterizing the dynamics of a structural unit inside a cage formed by other units, and manifested as the nearly constant loss shown in the frequency dependent susceptibility. We make the connection of f0 to the non-exponentiality parameter n in the Kohlrausch stretched exponential correlation function of the structural α-relaxation function, ϕ(t)=exp[-(t/τα)(1-n)]. This connection follows from the fact that both f0 and n are determined by the inter-particle potential, and 1/f0 or (1 - f0) and n both increase with anharmonicity of the potential. A well tested result from the Coupling Model is used to show that τß is completely determined by τα and n. From the string of relations, (i) K/G or νPoisson with 1/f0 or (1 - f0), (ii) 1/f0 or (1 - f0) with n, and (iii) τα and n with τß, we arrive at the desired relation between K/G or νPoisson and τß. On combining this relation with that between ductility and τß, we have finally an explanation of the empirical correlation between ductility and the Poisson's ratio νPoisson or K/G based on microscopic dynamical properties.

Single ambipolar OECT-based inverter with volatility and nonvolatility on demand.

Organic electrochemical transistor (OECT)-based inverter introduces new prospects for energy-efficient brain-inspired artificial intelligence devices. Here, we report single-component OECT-based inverters by incorporating ambipolar p(gDPP-V). Notably, p(gDPP-V) shows state-of-the-art ambipolar OECT performances in both conventional (p/n-type mode transconductance of 29/25 S cm-1) and vertical (transconductance of 297.2/292.4 µS µm-2 under p/n operation) device architectures. Especially, the resulting highly stable vertical OECT-based inverter shows a high voltage gain of 105 V V-1 under a low driving voltage of 0.8 V. The inverter exhibits undiscovered voltage-regulated dual mode: volatile receptor and nonvolatile synapse. Moreover, applications of physiology signal recording and demonstrations of NAND/NOR logic circuits are investigated within the volatile feature, while neuromorphic simulations with a convolutional neural network and image memorizing capabilities are explored under the nonvolatile behavior. The ambipolar OECT-based inverter, capable of both volatile and nonvolatile operations, provides possibilities for the applications of reconfigurable complementary logic circuits in novel neuromorphic computing paradigms.

First-principles structural design of superhard material of ZrB4.

Using the first-principles calypso algorithm for crystal structure prediction, we have predicted two orthorhombic Cmcm and Amm2 structures of ZrB4, which are energetically much superior to the previously proposed WB4-, CrB4-, and MoB4-type structures and stable against decompression into a mixture of Zr and B at ambient pressure. The two orthorhombic structures consist of a hexagonal B ring and ZrB12 units connected by edges and one hexagonal B ring in Cmcm and Amm2 structure, respectively. The calculated large shear modulus (e.g., 229 GPa) and high hardness (42.8 GPa for Cmcm and 42.6 GPa for Amm2) reveal that they are potentially superhard materials. The high hardness is attributed to a stacking of B-Zr-B "sandwiches" layers linked by strong covalent B-B bonding.

Dielectric relaxation of long-chain glass-forming monohydroxy alcohols.

The dielectric relaxation of two long-chain glass forming monohydroxy alcohols, 2-butyl-1-octanol and 2-hexyl-1-decanol, is studied at low temperature. Remarkable broadening from the pure Debye relaxation is identified for the slowest dynamics, differing from the dielectric spectra of short-chain alcohols. The broadening of the Debye-like relaxation in the two liquids develops as temperature increases, and the approaching of the Debye-like and structural relaxation widths is shown. Similar results are observed in the dielectric spectra of dilute 2-ethyl-1-hexanol in either 2-hexyl-1-decanol or squalane. The results of the liquids and mixtures reveal a correlation between the broadening and the Debye-like relaxation strength. Molecular associations in monohydroxy alcohols are discussed with the modification of the Debye relaxation.

Debye-type dielectric relaxation in glass-forming 3-methylthio-1-hexanol.

The dielectric relaxation of a substituted monohydroxy alcohol, 3-methylthio-1-hexanol, is studied in the highly viscous regime near the glass transition. The Debye relaxation is detected in the dielectric spectra showing the slowest and strongest relaxation dynamics. The calorimetric and dielectric measurements of the liquid and the mixtures with a Debye liquid (2-ethyl-1-hexanol) and a non-Debye liquid (2-ethylhexylamine) reproduce the dynamic characters of the relaxations in monohydroxy alcohols. The Debye relaxation strength and time of 3-methylthio-1-hexanol do not change much compared with 2-ethyl-1-hexanol, while the structural relaxation strength shows a considerable enhancement accompanied by an increase in relaxation time, indicative of a reduction in the dynamic separation between the Debye and structural relaxations. The experimental results allow for the examination of the structural models proposed for the Debye relaxation.

Pressure-induced pseudoatom bonding collapse and isosymmetric phase transition in Zr2Cu: first-principles predictions.

The structural evolution of tetragonal Zr2Cu has been investigated under high pressures up to 70 GPa by means of density functional theory. Our calculations predict a pressure-induced isosymmetric transition where the tetragonal symmetry (I4/mmm) is retained during the entire compression as well as decompression process while its axial ratio (c/a) undergoes a transition from ~3.5 to ~4.2 at around 35 GPa with a hysteresis width of about 4 GPa accompanied by an obvious volume collapse of 1.8% and anomalous elastic properties such as weak mechanical stability, dramatically high elastic anisotropy, and low Young's modulus. Crystallographically, the tetragonal axial ratio shift renders this transition analogous to a simple bcc-to-fcc structural transition, which implies it might be densification-driven. Electronically, the ambient Zr2Cu is uncovered with an intriguing pseudo BaFe2As2-type structure, which upon the phase transition undergoes an electron density topological change and collapses to an atomic-sandwich-like structure. The pseudo BaFe2As2-type structure is demonstrated to be shaped by hybridized dxz + yz electronic states below Fermi level, while the high pressure straight Zr-Zr bonding is accommodated by electronic states near Fermi level with dx(2) - y(2) dominant features.

Depicting Defects in Metallic Glasses by Atomic Vibrational Entropy.

Due to the chaotic structure of amorphous materials, it is challenging to identify defects in metallic glasses. Here we tackle this problem from a thermodynamic point of view using atomic vibrational entropy, which represents the inhomogeneity of atomic contributions to vibrational modes. We find that the atomic vibrational entropy is correlated to the vibrational mean-square displacement and polyhedral volume of atoms, revealing the critical role of vibrational entropy in bridging dynamics, thermodynamics, and structure. On this method, the local vibrational entropy obtained by coarse-graining the atomic vibrational entropy in space can distinguish more effectively between liquid-like and solid-like atoms in metallic glasses and establish the correlation between the local vibrational entropy and the structure of metallic glasses, offering a route to predict the plastic events from local vibrational entropy. The local vibration entropy is a good indicator of thermally activated and stress-driven plastic events, and its predictive ability is better than that of the structural indicators.

Kinetic fragility of binary and ternary glass forming liquid mixtures.

The experimental studies of liquid fragility in miscible binary and ternary glass forming mixtures reveal a general observation of the negative deviation in fragility upon mixing from the linear average of those of the components. Further analyses from ideal, near ideal to non-ideal mixing modes show that the deviation magnitude does not increase monotonically with mixing enthalpy, and a moderate intermolecular interaction would generate a largest reduction in fragility. Four eutectic systems, methyl-o-toluate-methyl-p-toluate, ZnCl(2)-AlCl(3), glycerol-water, and fructose-water, are studied to locate the composition where the largest fragility deviation occurs in phase diagrams. It is found that the compositions with the fragility minima do not coincide with the eutectic points. The results partly explain the experimental observation that the best glass forming region is not located at the eutectic composition.

High-throughput screening of single metal atom anchored on N-doped boron phosphide for N2 reduction.

Developing eco-friendly and highly-efficient catalysts for the electrochemical nitrogen reduction reaction (NRR) under ambient conditions to replace the energy-intensive and environment-polluting Haber-Bosch process is of great significance, while remaining a long-standing challenge in the field of energy conversion today. Herein, through the first principles high-throughput screening, we systematically investigated the catalytic activity of a series of single metal atom immobilized on N-doped boron phosphide (N3-BP) for N2 reduction, denoted as MN3-BP. In particular, a "four-step" screening strategy, involving the structural stability, N2 chemisorption, low energy cost, as well as good selectivity, was adopted for the stringent screening of the promising MN3-BP candidates for NRR. Our results unveil that among these candidates, MoN3-BP eventually stands out, benefiting from its high selectivity and activity, as well as accompanying a considerably favorable limiting potential of -0.25 V for NRR. More impressively, the NRR activity origin of various candidates was revealed by the descriptor φ and ICOHP. Overall, our work not only accelerates the discovery of SACs for converting N2 into sustainable NH3 but also provides an exciting impetus for the rational design of NRR catalysts with high stability, high activity, and high selectivity.