Advances and Challenges in Interfacial Binding Forces for Electrocatalysts.

As a practical chemical energy conversion technology, electrocatalysis could be used in fields of energy conversion and environmental protection. In recent years, significant research efforts have been devoted to the design and development of high-performance electrocatalysts because the rational design of catalysts is crucial for enhancing electrocatalytic performance. Creating electrocatalysts by forming interactions between different components at the interface is an important means of controlling and improving performance. Therefore, several common interfacial binding forces used for synthesizing electrocatalysts was systematically summarized in this review for the first time. The discussion revolves around the crucial roles these binding forces play in various electrocatalytic reaction processes. Various characterization techniques capable of proving the existence of these interfacial binding forces was also involved in the review. Finally, some prospects and challenges for designing and researching materials through the utilization of interfacial binding forces were presented.

Frictional Properties of Two-Dimensional Materials: Data-Driven Machine Learning Predictive Modeling.

Friction, typically associated with reduced efficiency and reliability of machines and devices, occurs when two objects are displaced against each other. This is a strongly material-dependent phenomenon, and the emergence of many 2D materials has opened up new opportunities to design systems with desired tribological properties. Here, we combine high throughput simulations and machine learning models to develop a statistical approach of adhesion, van der Waals, and corrugation energies of a large dataset of monolayered materials. The machine learning models are used to predict these closely related to friction energetic properties and link them to easily accessible atomistic and monolayer features. This approach elevates the materials' perspective of frictional properties. It demonstrates that data-driven models are extremely useful in discovering important structure-property functionalities for frictional property interpretations as a fruitful route toward desired tribological materials.

Mechanical and thermoelectric properties of ZrX2 and HfX2 (X = S and Se) from Van der Waals density-functional theory.

The structural, mechanical, and thermoelectric characteristics of layered transition metal dichalcogenides MX2 (M = Zr, Hf; X = S, Se) have been studied using density functional theory along with van der Waals correction. The exchange-correlation functional, enhanced with corrections for van der Waals interactions, has been evaluated for the hexagonal bulk structures of these materials. The analysis of elastic properties reveals that these compounds exhibit brittleness at zero pressure and conform to Born's criteria for mechanical stability. Examination of elastic constants and moduli suggests that the compounds possess reasonable machinability, moderate hardness, and anisotropy in terms of sound velocity. Transport properties, including the Seebeck coefficient, electrical conductivity, thermal conductivity, and power factor, have been computed using the semi-classical Boltzmann theory implemented in the BoltzTraP code. All investigated compounds exhibit excellent thermoelectric performance at high temperatures. This result suggests that our compounds are highly promising candidate for practical utilization in the thermoelectric scope.

Weakly bound complexes of 1,2,3-triazole with nitrogen and carbon dioxide isolated in solid argon: A combined FT-IR matrix isolation and theoretical investigation.

Matrix isolation FT-IR spectroscopy was combined with quantum-chemical calculations in order to characterize complexes of 1,2,3-triazole (3TR) with nitrogen and carbon dioxide. Geometries of the possible 1:1 and 1:2 complexes, as well as 3TR dimers, were optimized at the DFT (B3LYP-D3) level of theory with the 6-311++G(3df,3pd) basis set. Six different 3TR⋯N2 structures of the 1:1 stoichiometry were optimized which are characterized by weak hydrogen bonds (N-H⋯N and C-H⋯N) and/or Van der Waals type interactions (N⋯C, N⋯N, N⋯π). Two the most stable geometries, both containing a N-H⋯N bridge, were identified experimentally in solid argon. As for 3TR⋯CO2 complexes, out of two minima located on the potential energy surface, only one with a strongly bent N-H⋯O hydrogen bond was detected in the matrix after deposition. In both cases, only annealing experiments at 32 K resulted in the formation of small amounts of 1:2 structures.

Layer-Polarized Anomalous Hall Effects from Inversion-Symmetric Single-Layer Lattices.

In the field of physics and materials science, the discovery of the layer-polarized anomalous Hall effect (LP-AHE) stands as a crucial development. The current research paradigm is rooted in topological or inversion-asymmetric valleytronic systems, making such a phenomenon rather rare. In this work, a universal design principle for achieving the LP-AHE from inversion-symmetric single-layer lattices is proposed. Through tight-binding model analysis, we demonstrate that by stacking into antiferromagnetic van der Waals bilayer lattices, the coupling physics between PT symmetry and vertical external bias can be realized. This coupling reveals the previously neutralized layer-locked Berry curvature, compelling the carriers to move in a specific direction within a given layer, thereby realizing the LP-AHE. Intriguingly, the chirality of the LP-AHE can be effectively switched by modulating the direction of vertical external bias. First-principles calculations validate this mechanism in bilayer T-FeCl2 and MnPSe3. Our results pave the way for new explorations of the LP-AHE.

Mitigating Surface Defects in Tin-Based Perovskite Films with α-Tocopherol for Enhanced Photovoltaic Performance.

Surface defects in tin-based perovskite films disrupt the periodic arrangement of atoms in crystals, making surface atoms more susceptible to interactions with water and oxygen molecules in the surrounding environment. The diffusion of oxygen ions into the perovskite interior leads to the formation of severe bulk defects, which compromises the performance of tin-based perovskite solar cells (PSCs). As a result, surface defects are recognized as the primary source of degradation and require special attention. In this study, α-Tocopherol (also known as vitamin E) into tin-based perovskite films is introduced. Experimental results show that because of its larger volume, α-Tocopherol does not enter the perovskite lattice. Instead, it forms van der Waals and hydrogen bond interactions with the formamidine ion (FA+) and the [SnI6]4- octahedron at the perovskite terminals. Through α-Tocopherol passivation, both surface and interior oxidation of the perovskite are significantly suppressed as α-Tocopherol firmly embeds itself on the perovskite surface. Density functional theory analysis confirms the inhibition of I─Sn antisite defects (ISn) and Sn interstitial defects (Sni), which possess deep trap states within the bandgap. Ultimately, it is demonstrated that α-Tocopherol enhances the power conversion efficiency (PCE) from 9.19% to 13.14% and prolongs the lifetime of tin-based PSCs to over 50 days.

Revisiting structural organization of proteins at high temperature from a network perspective.

Interactions between distantly placed amino acids in the primary chain (long-range) play a very crucial role in the formation and stabilization of the tertiary structure of a protein, while interactions between closely placed amino acids in the primary chain (short-range) mostly stabilize the secondary structures. Every protein needs to maintain marginal stability in order to perform its physiological functions in its native environment. The requirements for this stability in mesophilic and thermophilic proteins are different. Thermophilic proteins need to form more interactions as well as more stable interactions to survive in the extreme environment, they live in. Here, we aim to find out how the interacting amino acids in three-dimensional space are positioned in the primary chains in thermophilic and mesophilic. How does this arrangement help thermophiles to maintain their structural integrity at high temperatures? Working on a dataset of 1560 orthologous pairs we perceive that thermophiles are not only enriched with long-range interactions, they feature bigger connected clusters and higher network densities compared to their mesophilic orthologs, at higher interaction strengths between the amino acids. Moreover, we have observed the enrichment of different types of interactions at different secondary structural regions.

Construction of the Stable Lubricant Film on One-Dimensional Cone-Structured Surfaces for Directional Liquid Transport.

Directional liquid transport along one-dimensional structures finds vast applications in fog harvest, liquid separation, sensing, chemical synthesis, and numerous other scenarios. Dynamically, the liquid transport speed is boosted by the driving force and retarded by the hysteresis from the liquid/substrate interface. A capillary force-relied lubricant film or a covalently attached polymer brush on the surface could increase liquid mobility temporarily by reducing the interfacial hysteresis. However, the easy depletion of the lubricant film and the stringent restriction of the substrate severely hamper droplet's directional transport in a long run. Herein, we report a feasible and durable hysteresis reduction design with the polymer-brush stabilized lubricating surface (PBSLS). The PBSLS is achieved through incorporating liquid-like polydimethylsiloxane brushes (b-PDMS) and the liquid PDMS oligomer (o-PDMS). The covalent attached b-PDMS "locks" the lubricant oil o-PDMS to the cone surface via strong intermolecular van der Waals force in between. The PBSLS on the cone surface can be sustained under constant shearing force from liquid transport for at least 6 h. A cone with such PBSLS shows increased ability of droplet transport and enhanced fog collection performance in the long run. This design supplies an effective way toward regulating macro-level interfacial performance through surface design on the molecular level.

Single-Atom Control of Single-Molecule van der Waals Junctions with Semimetallic Transition Metal Dichalcogenide Electrodes.

Electrodes play an essential role in controlling electrode-molecule coupling. However, conventional metal electrodes require linkers to anchor the molecule. Van der Waals interaction offers a versatile strategy to connect the electrode and molecule without anchor groups. Except for graphene, the potential of other materials as electrodes to fabricate van der Waals molecular junctions remains unexplored. Herein, we utilize semimetallic transition metal dichalcogenides (TMDCs) 1T'-WTe2 as electrodes to fabricate WTe2/metalated tetraphenylporphyrin (M-TPP)/WTe2 junctions via van der Waals interaction. Compared with chemically bonded Au/M-TPP/Au junctions, the conductance of these M-TPP van der Waals molecular junctions is enhanced by ∼736%. More importantly, WTe2/M-TPP/WTe2 junctions exhibit the tunable conductance from 10-3.29 to 10-4.44 G0 (1.15 orders of magnitude) via single-atom control, recording the widest tunable range of conductance for M-TPP molecular junctions. Our work demonstrates the potential of two-dimensional TMDCs for constructing highly tunable and conductive molecular devices.

Influence of ligands within Al-based metal-organic frameworks for selective separation of methane from unconventional natural gas.

Efficient CH4/N2 separation from unconventional natural gas is vital for both energy recycling and climate change control. Figuring out the reason for the disparity between ligands in the framework and CH4 is the crucial problem for developing adsorbents in PSA progress. In this study, a series of eco-friendly Al-based MOFs, including Al-CDC, Al-BDC, CAU-10, and MIL-160, were synthesized to investigate the influence of ligands on CH4 separation through experimental and theoretical analyses. The hydrothermal stability and water affinity of synthetic MOFs were explored through experimental characterization. The active adsorption sites and adsorption mechanisms were investigated via quantum calculation. The results manifested that the interactions between CH4 and MOFs materials were affected by the synergetic effects of pore structure and ligand polarities, and the disparities of ligands within MOFs determined the separation efficiency of CH4. Especially, the CH4 separation performance of Al-CDC with high sorbent selection (68.56), moderate isosteric adsorption heat for CH4 (26.3 kJ/mol), and low water affinity (0.1 g/g at 40% RH) was superior to most porous adsorbents, which was attributed to its nanosheet structure, proper polarity, reduced local steric hindrance, and extra functional groups. The analysis of active adsorption sites indicated that hydrophilic carboxyl groups and hydrophobic aromatic ring were the dominant CH4 adsorption sites for liner ligands and bent ligands, respectively. The methylene groups with saturated C-H bonds enhanced the wdV interaction between ligands and CH4, resulting in the highest binding energy of CH4 for Al-CDC. The results provided valuable guidance for the design and optimization of high-performance adsorbents for CH4 separation from unconventional natural gas.

Voltage-Modulated van der Waals Interaction in Single-Molecule Junctions.

Understanding how molecular geometry affects the electronic properties of single-molecule junctions experimentally has been challenging. Typically, metal-molecule-metal junctions are measured using a break-junction method where electrode separation is mechanically evolving during measurement. Here, to probe the impact of the junction geometry on conductance, we apply a sinusoidal modulation to the molecular junction electrode position. Simultaneously, we probe the nonlinearity of the current-voltage characteristics of each junction through a modulation in the applied bias at a different frequency. In turn, we show that junctions formed with molecules that have different molecule-electrode interfaces exhibit statistically distinguishable Fourier-transformed conductances. In particular, we find a marked bias dependence for the modulation of junctions where transmission is mediated thorough the van der Waals (vdW) interaction. We attribute our findings to voltage-modulated vdW interactions at the single-molecule level.

Van der Waals Multilayer Heterojunction for Low-Voltage Organic RGB Area-Emitting Transistor Array.

Organic light-emitting transistors (OLETs) have garnered considerable attention from academy and industry due to their potential applications in next-generation display technologies, multifunctional devices, and organic electrically pumped lasers. However, overcoming the trade-offs among power consumption, external quantum efficiency (EQE), and uniform area emission remains a long-standing issue for OLETs. Herein, a van der Waals multilayer heterojunction methodology is proposed to enhance the layer-to-layer interfacial interaction and contact, resulting in better dipole shielding, carrier transport, exciton recombination, and current density distribution. The prepared multilayer heterojunction OLET (MLH-OLET) array shows uniform and bright RGB area emission and low operating voltage (<30 V among the lowest applied voltage of reported lateral LETs). Additionally, a high brightness under area emission of 1060 cd m-2 , a high EQE value of 0.85%, and a high loop stability (over 380 cycles, outperforming state-of-the-art OLETs) indicate that the proposed multilayer heterojunction is obviously superior to the reported lateral device configuration. The van der Waals multilayer heterojunction developed for the preparation of OLET arrays sufficiently meets the low-voltage, high-performance, and low-cost requirements of future display technologies.

Structure and IR spectroscopic properties of complexes of 1,2,4-triazole and 3-amino-1,2,4-triazole with dinitrogen isolated in solid argon.

Complexes of 1,2,4-triazole (TR) and 3-amino-1,2,4-triazole (AT) with N2 were studied computationally employing MP2 and B3LYPD3 methods and experimentally by FTIR matrix isolation technique. The results show that both triazoles interact specifically with dinitrogen in several different ways. For the 1:1 complexes of 1,2,4-triazole five stable minima were located on the potential energy surface. The most stable of them comprises a weak hydrogen bond formed between the NH group of the ring and the lone pair of the nitrogen molecule. The second most stable structure is bound by the N⋯π bond formed between one of the N atoms of the N2 molecule and the triazole ring. Three other complexes are stabilized by the C-H⋯N and N⋯N van der Waals interactions. In the case of 3-amino-1,2,4-triazole, the two most stable dinitrogen complexes are analogous to those found for the 1,2,4-triazole and involve N-H⋯N and N⋯π bonds. In other structures amino or CH groups act as proton donors to the N2 molecule. The N⋯N van der Waals interactions are also present. The analysis of the infrared spectra of low temperature matrices containing TR or AT and dinitrogen indicates that in both systems mostly 1:1 hydrogen-bonded complexes with the NH group interacting with N2 are present in solid argon.

Fullerene Derivatives (CN-[OH]ß) and Single-Walled Carbon Nanotubes Modelled as Transporters for Doxorubicin Drug in Cancer Therapy.

Carbon nanomaterials have received increasing attention in drug-delivery applications because of their distinct properties and structures, including large surface areas, high conductivity, low solubility in aqueous media, unique chemical functionalities, and stability at the nano-scale size. Particularly, they have been used as nano-carriers and mediators for anticancer drugs such as Cisplatin, Camptothecin, and Doxorubicin. Cancer has become the most challenging disease because it requires sophisticated therapy, and it is classified as one of the top killers according to the World Health Organization records. The aim of the current work is to study and investigate the mechanism of combination between single-walled carbon nanotubes (SWCNTs) and fullerene derivatives (CN-[OH]ß) as mediators, and anticancer agents for photodynamic therapy directly to destroy the infected cells without damaging the normal ones. Here, we obtain a bio-medical model to determine the efficiency of the usefulness of Doxorubicin (DOX) as an antitumor agent conjugated with SWCNTs with variant radii r and fullerene derivative (CN-[OH]ß). The two sub-models are obtained mathematically to evaluate the potential energy arising from the DOX-SWCNT and DOX-(CN-[OH]ß) interactions. DOX modelled as two-connected spheres, small and large, each interacting with different SWCNTs (variant radii r) and fullerene derivatives CN-[OH]ß, formed based on the number of carbon atoms (N) and the number of hydroxide molecules (OH) (ß), respectively. Based on our obtained results, we find that the most favorable carbon nanomaterial is the SWCNT (r = 15.27 Å), followed by fullerene derivatives CN-(OH)22, CN-(OH)20, and CN-(OH)24, with minimum energies of -38.27, -33.72, -32.95, and -29.11 kcal/mol.

A Strategy for Polar Crystals with Dipolar Heterohelicenes.

Polar crystals have attracted interest for the applications to polar materials with piezo- and pyroelectricity, and second harmonic generation. Despite their potential utility for flexible polar materials, a strategy for ordering polar helicenes has remained elusive. Here, we demonstrate the creation of polar crystals with unsymmetrically substituted aza[5]helicenes tuned by substituents. The unsymmetric aza[5]helicenes have been prepared through regioselective mono-protiodesilylations. We disclose that triisopropylsilyl-substituted derivatives show 1D chain columnar packings. In particular, enantiopure crystals showed spontaneous polarization. Optical and single-crystal X-ray diffraction experiments with other derivatives, as well as theoretical calculations, revealed that the presence of triisopropylsilyl or electron-withdrawing aryl substituents is essential for forming the 1D chain columnar structure. Hirshfeld surface analyses further showed that CH-π interactions between 1D chain columns regulate the polar assembly. Finally, we determined the polarizability of the nitro derivative by ab initio calculation to be 4.53 µC/cm2 . This value corroborates the first example of a spontaneously polar crystal of helicenes. We believe that this study will contribute to the development of polar materials from organic molecules.

Di-tert-butyl-tin(IV)-hydroxide-iodide, t Bu2Sn(OH)I, the last missing member in the series of pure di-tert-butyl-tin(IV)-hydroxide-halides.

The crystal structure of di-tert-butyl-hydroxido-iodido-tin(IV), [Sn(C4H9)2I(OH)] or t Bu2Sn(OH)I, consists of dimeric, centrosymmetric mol-ecules exhibiting the typical structural features of diorganotin(IV)-hydroxide-halides, R 2Sn(OH)Hal. Two trigonal-bipyramidally coordinated tin(IV) atoms are bridged via two hydroxyl groups, resulting in a planar, four-membered {Sn-O}2 ring of rhombic shape, with acute angles at tin, obtuse angles at oxygen and two different Sn-O distances depending whether the oxygen atom adopts an axial or equatorial position at the tin(IV) atom. In contrast to its fluorine, chlorine and bromine homologues, no hydrogen bonds between the OH group and the halide atom exist, confining the inter-molecular inter-actions to van der Waals forces.

Modified Protein-Water Interactions in CHARMM36m for Thermodynamics and Kinetics of Proteins in Dilute and Crowded Solutions.

Proper balance between protein-protein and protein-water interactions is vital for atomistic molecular dynamics (MD) simulations of globular proteins as well as intrinsically disordered proteins (IDPs). The overestimation of protein-protein interactions tends to make IDPs more compact than those in experiments. Likewise, multiple proteins in crowded solutions are aggregated with each other too strongly. To optimize the balance, Lennard-Jones (LJ) interactions between protein and water are often increased about 10% (with a scaling parameter, λ = 1.1) from the existing force fields. Here, we explore the optimal scaling parameter of protein-water LJ interactions for CHARMM36m in conjunction with the modified TIP3P water model, by performing enhanced sampling MD simulations of several peptides in dilute solutions and conventional MD simulations of globular proteins in dilute and crowded solutions. In our simulations, 10% increase of protein-water LJ interaction for the CHARMM36m cannot maintain stability of a small helical peptide, (AAQAA)3 in a dilute solution and only a small modification of protein-water LJ interaction up to the 3% increase (λ = 1.03) is allowed. The modified protein-water interactions are applicable to other peptides and globular proteins in dilute solutions without changing thermodynamic properties from the original CHARMM36m. However, it has a great impact on the diffusive properties of proteins in crowded solutions, avoiding the formation of too sticky protein-protein interactions.

One-Dimensional Atomic Chains for Ultimate-Scaled Electronics.

The continuous downscaling of semiconducting channels in transistors has driven the development of modern electronics. However, with the component transistors becoming smaller and denser on a single chip, the continued downscaling progress has touched the physical limits. In this Perspective, we suggest that the emerging one-dimensional (1D) material system involving inorganic atomic chains (ACs) that are packed by van der Waals (vdW) interactions may tackle this issue. Stemming from their 1D crystal structures and naturally terminated surfaces, 1D ACs could potentially shrink transistors to atomic-scale diameters. Also, we argue that 1D ACs with few-atom widths allow us to revisit 1D materials and uncover physical properties distinct from conventional materials. These ultrathin 1D AC materials demand substantive attention. They may bring opportunities to develop ultimate-scaled AC-based electronic, optoelectronic, thermoelectric, spintronic, memory devices, etc.

Interlayer Coupling: An Additional Degree of Freedom in Two-Dimensional Materials.

Due to their layered nature, two-dimensional nanomaterials can stack into artificial material systems, with van der Waals interaction between the adjacent constituent layers. In such heterostructures, the physical properties are largely affected by the interlayer coupling and can thus be effectively tuned by a number of means. In this Perspective, we highlight four such experimental approaches: stacking order, electric field, intercalation, and pressure, and we discuss challenges and opportunities in future studies for van der Waals heterostructures.

SuFEx-Enabled Elastic Polysulfates for Efficient Removal of Radioactive Iodomethane and Polar Aprotic Organics through Weak Intermolecular Forces.

Capturing radioactive iodomethane and its vapors is a major challenge due to its low adsorption capacity. Herein, we have developed for the first time a pyridine-entrapped elastic crosslinked polysulfate gel (pyridine/TPC-cPS) as an efficient absorbent for iodomethane capture. Each pyridine-encased TPC-cPS network cell acts as a mini-reactor for salt formation between pyridine and iodomethane. The yield reaches up to 96.65 % and traps saturated iodomethane vapor of 1.573 g gpyridine/TPC-cPS -1 (equivalent to 18.103 g gTPC-cPS -1 ), which is the highest capacity reported to date. Both experiments and molecular dynamics simulations reveal that the unusual adsorption of polysulfate for polar aprotic organics can be attributed to the fact that the electrostatic interactions between the polar group (O=S=O) in the polymer backbone and the polar groups in the organic molecules fixed the solvent in the polymer matrix, while the van der Waals forces between the nonpolar groups in the polymer and molecules induced swelling.