Growth of diamond in liquid metal at 1 atm pressure.

Natural diamonds were (and are) formed (thousands of million years ago) in the upper mantle of Earth in metallic melts at temperatures of 900-1,400 °C and at pressures of 5-6 GPa (refs. 1,2). Diamond is thermodynamically stable under high-pressure and high-temperature conditions as per the phase diagram of carbon3. Scientists at General Electric invented and used a high-pressure and high-temperature apparatus in 1955 to synthesize diamonds by using molten iron sulfide at about 7 GPa and 1,600 °C (refs. 4-6). There is an existing model that diamond can be grown using liquid metals only at both high pressure and high temperature7. Here we describe the growth of diamond crystals and polycrystalline diamond films with no seed particles using liquid metal but at 1 atm pressure and at 1,025 °C, breaking this pattern. Diamond grew in the subsurface of liquid metal composed of gallium, iron, nickel and silicon, by catalytic activation of methane and diffusion of carbon atoms into and within the subsurface regions. We found that the supersaturation of carbon in the liquid metal subsurface leads to the nucleation and growth of diamonds, with Si playing an important part in stabilizing tetravalently bonded carbon clusters that play a part in nucleation. Growth of (metastable) diamond in liquid metal at moderate temperature and 1 atm pressure opens many possibilities for further basic science studies and for the scaling of this type of growth.

An Amiable Design of Cobalt Single Atoms as the Active Sites for Oxygen Evolution Reaction in Desalinated Seawater.

Green fuel from water splitting is hardcore for future generations, and the limited source of fresh water (<1%) is a bottleneck. Seawater cannot be used directly as a feedstock in current electrolyzer techniques. Until now single atom catalysts were reported by many synthetic strategies using notorious chemicals and harsh conditions. A cobalt single-atom (CoSA) intruding cobalt oxide ultrasmall nanoparticle (Co3 O4 USNP)-intercalated porous carbon (PC) (CoSA-Co3 O4 @PC) electrocatalyst was synthesized from the waste orange peel as a single feedstock (solvent/template). The extended X-ray absorption fine structure spectroscopy (EXAFS) and theoretical fitting reveal a clear picture of the coordination environment of the CoSA sites (CoSA-Co3 O4 and CoSA-N4 in PC). To impede the direct seawater corrosion and chlorine evolution the seawater has been desalinated (Dseawater) with minimal cost and the obtained PC is used as an adsorbent in this process. CoSA-Co3 O4 @PC shows high oxygen evolution reaction (OER) activity in transitional metal impurity-free (TMIF) 1 M KOH and alkaline Dseawater. CoSA-Co3 O4 @PC exhibits mass activity that is 15 times higher than the commercial RuO2 . Theoretical interpretations suggest that the optimized CoSA sites in Co3 O4 USNPs reduce the energy barrier for alkaline water dissociation and simultaneously trigger an excellent OER followed by an adsorbate evolution mechanism (AEM).

Growth Kinetics of Graphene on Cu(111) Foils from Methane, Ethyne, Ethylene, and Ethane.

Chemical vapor deposition of carbon precursors on Cu-based substrates at temperatures exceeding 1000 °C is currently a typical route for the scalable synthesis of large-area high-quality single-layer graphene (SLG) films. Using molecules with higher activities than CH4 may afford lower growth temperatures that might yield fold- and wrinkle-free graphene. The kinetics of growth of graphene using hydrocarbons other than CH4 are of interest to the scientific and industrial communities. We measured the growth rates of graphene islands on Cu(111) foils by using C2H2, C2H4, C2H6 and CH4, respectively (each mixed with H2). From such kinetics data we obtain the activation enthalpy (ΔH≠) of graphene growth as shown in parentheses (C2H2 (0.93±0.09 eV); C2H4 (2.05±0.19 eV); C2H6 (2.50±0.11 eV); CH4 (4.59±0.26 eV)); C2Hy (y=2, 4, 6) show similar growth behavior but CH4 is different. Computational fluid dynamics and density functional theory simulations suggest that C2Hy differs from CH4 due to different values of adsorption energy and the lifetime of relevant carbon precursors on the Cu(111) surface. Combining experimental and simulation results, we find that the rate determining step (RDS) is the dissociation of the first C-H bond of CH4 molecules in the gas phase, while the RDS using C2Hy is the first dehydrogenation of adsorbed C2Hy that happens with assistance of H atoms adsorbed on the Cu(111) surface. By using C2H2 as the carbon precursor, high-quality single-crystal adlayer-free SLG films are achieved on Cu(111) foils at 900 °C.

Cobalt-Porphyrin-Based Covalent Organic Frameworks with Donor-Acceptor Units as Photocatalysts for Carbon Dioxide Reduction.

Covalent organic frameworks (COFs) have emerged as a promising platform for photocatalysts. Their crystalline porous nature allows comprehensive mechanistic studies of photocatalysis, which have revealed that their general photophysical parameters, such as light absorption ability, electronic band structure, and charge separation efficiency, can be conveniently tailored by structural modifications. However, further understanding of the relationship between structure-property-activity is required from the viewpoint of charge-carrier transport, because the charge-carrier property is closely related to alleviation of the excitonic effect. In the present study, COFs composed of a fixed cobalt (Co) porphyrin (Por) centered tetraamine as an acceptor unit with differently conjugated di-carbaldehyde based donor units, such as benzodithiophene (BDT), thienothiophene (TT), or phenyl (TA), were synthesized to form Co-Por-BDT, Co-Por-TT, or Co-Por-TA, respectively. Their photocatalytic activity for reducing carbon dioxide into carbon monoxide was in the order of Co-Por-BDT>Co-Por-TT>Co-Por-TA. The results indicated that the excitonic effect, associated with their charge-carrier densities and π-conjugation lengths, was a significant factor in photocatalysis performance.

Geomimetic Hydrothermal Synthesis of Polyimide-Based Covalent Organic Frameworks.

Despite its abundance, water is not widely used as a medium for organic reactions. However, under geothermal conditions, water exhibits unique physicochemical properties, such as viscosity and a dielectric constant, and the ionic product become similar to those of common organic solvents. We have synthesized highly crystalline polyimide-based covalent organic frameworks (PICs) under geomimetic hydrothermal conditions. By exploiting triphenylene-2,3,6,7,10,11-hexacarboxylic acid in combination with various aromatic diamines, PICs with various pore dimensions and crystallinities were synthesized. XRD, FT-IR, and DFT calculations revealed that the solubility of the oligomeric intermediates under hydrothermal conditions affected the stacking structures of the crystalline PICs. Furthermore, the synthesized PICs demonstrate promising potential as an anode material in lithium-ion batteries owing to its unique redox-active properties and high surface area.

Ultrasensitive Plasmon-Free Surface-Enhanced Raman Spectroscopy with Femtomolar Detection Limit from 2D van der Waals Heterostructure.

Two-dimensional (2D) materials have been promoted as an ideal platform for surface-enhanced Raman spectroscopy (SERS), as they mitigate the drawbacks of noble metal-based SERS substrates. However, the inferior limit of detection has limited the practical applicability of 2D material-based SERS substrates. Here, we synthesize uniform large-area ReOxSy thin films via solution-phase deposition without post-treatments and demonstrate a graphene/ReOxSy vertical heterostructure as an ultrasensitive SERS platform. The electronic structure of ReOxSy can be modulated by changing the oxygen concentration in the lattice structure, obtaining efficient complementary resonance effects between ReOxSy and the probe molecule. In addition, the oxygen atoms in the ReOxSy lattice generate a dipole moment on the thin-film surface, which increases the electron transition probability. These synergistic effects outstandingly enhance the Raman effect in the ReOxSy thin film. When ReOxSy forms a vertical heterostructure on a graphene as the SERS substrate, the enhanced charge-transfer and exciton resonances improve the limit of detection to the femtomolar level, while achieving remarkable flexibility, reproducibility, and operational stability. Our results provide important insights into 2D material-based ultrasensitive SERS based on chemical mechanisms.

Zwitterionic Conjugated Surfactant Functionalization of Graphene with pH-Independent Dispersibility: An Efficient Electron Mediator for the Oxygen Evolution Reaction in Acidic Media.

The functionalization of graphene has been extensively used as an effective route for modulating the surface property of graphene, and enhancing the dispersion stability of graphene in aqueous solutions via functionalization has been widely investigated to expand its use for various applications across a range of fields. Herein, an effective approach is described for enhancing the dispersibility of graphene in aqueous solutions at different pH levels via non-covalent zwitterion functionalization. The results show that a surfactant with electron-deficient carbon atoms in its backbone structure and large π-π interactive area enables strong interactions with graphene, and the zwitterionic side terminal groups of the molecule support the dispersibility of graphene in various pH conditions. Experimental and computational studies confirm that perylene diimide amino N-oxide (PDI-NO) allows efficient functionalization and pH-independent dispersion of graphene enabled by hydration repulsion effects induced by PDI-NO. The PDI-NO functionalized graphene is successfully used in the oxygen evolution reaction as an electron mediator for boosting the electrocatalytic activity of a Ru-based polyoxometalate catalyst in an acidic medium. The proposed strategy is expected to bring significant advances in producing highly dispersible graphene in aqueous medium with pH-independent stability, thus broadening the application range of graphene.

Edge functionalized graphene nanoribbons with tunable band edges for carrier transport interlayers in organic-inorganic perovskite solar cells.

Organic based graphene nanoribbons (GNRs) can be good candidates as carrier extraction interlayers for organic/inorganic hybrid perovskite solar cells, owing to the possibility of tuning the band edge energy levels through varying the width and the type of edge functionalization. By using the density functional theory (DFT) method, the electronic structures of H or F edge functionalized armchair type GNRs on MAPbI3(001) are calculated. It is shown that the electronic structure of H- or F-passivated GNRs is almost undisrupted by the non-covalent interaction with the PbI2 surface layer of MAPbI3(001), thereby one can tune the width and edge chemistry of GNRs to enhance the carrier extraction or blocking. Especially all H-GNRs five to ten carbon atoms wide exhibit good matching for hole extraction, while F-GNRs require a specific width for electron extraction. Exploiting the unzipping synthesis of carbon nanotubes in the solution phase, our result provides a facile strategy for efficient carrier extraction.

Unveiling 79-Year-Old Ixene and Its BN-Doped Derivative.

Polycyclic aromatic hydrocarbons (PAHs) are key components of organic electronics. The electronic properties of these carbon-rich materials can be controlled through doping with heteroatoms such as B and N, however, few convenient syntheses of BN-doped PAHs have been reported. Described herein is the rationally designed, two-step syntheses of previously unknown ixene and BN-doped ixene (B2 N2 -ixene), and their characterizations. Compared to ixene, B2 N2 -ixene absorbs longer-wavelength light and has a smaller electrochemical energy gap. In addition to its single-crystal structure, scanning tunneling microscopy revealed that B2 N2 -ixene adopts a nonplanar geometry on a Au(111) surface. The experimentally obtained electronic structure of B2 N2 -ixene and the effect of BN-doping were confirmed by DFT calculations. This synthesis enables the efficient and convenient construction of BN-doped systems with extended π-conjugation that can be used in versatile organic electronics applications.

Surface-Effect-Induced Optical Bandgap Shrinkage in GaN Nanotubes.

We investigate nontrivial surface effects on the optical properties of self-assembled crystalline GaN nanotubes grown on Si substrates. The excitonic emission is observed to redshift by ∼100 meV with respect to that of bulk GaN. We find that the conduction band edge is mainly dominated by surface atoms, and that a larger number of surface atoms for the tube is likely to increase the bandwidth, thus reducing the optical bandgap. The experimental findings can have important impacts in the understanding of the role of surfaces in nanostructured semiconductors with an enhanced surface/volume ratio.

Density functional theory based study of molecular interactions, recognition, engineering, and quantum transport in π molecular systems.

CONSPECTUS: In chemical and biological systems, various interactions that govern the chemical and physical properties of molecules, assembling phenomena, and electronic transport properties compete and control the microscopic structure of materials. The well-controlled manipulation of each component can allow researchers to design receptors or sensors, new molecular architectures, structures with novel morphology, and functional molecules or devices. In this Account, we describe the structures and electronic and spintronic properties of π-molecular systems that are important for controlling the architecture of a variety of carbon-based systems. Although DFT is an important tool for describing molecular interactions, the inability of DFT to accurately represent dispersion interactions has made it difficult to properly describe π-interactions. However, the recently developed dispersion corrections for DFT have allowed us to include these dispersion interactions cost-effectively. We have investigated noncovalent interactions of various π-systems including aromatic-π, aliphatic-π, and non-π systems based on dispersion-corrected DFT (DFT-D). In addition, we have addressed the validity of DFT-D compared with the complete basis set (CBS) limit values of coupled cluster theory with single, double, and perturbative triple excitations [CCSD(T)] and Møller-Plesset second order perturbation theory (MP2). The DFT-D methods are still unable to predict the correct ordering in binding energies within the benzene dimer and the cyclohexane dimer. Nevertheless, the overall DFT-D predicted binding energies are in reasonable agreement with the CCSD(T) results. In most cases, results using the B97-D3 method closely reproduce the CCSD(T) results with the optimized energy-fitting parameters. On the other hand, vdW-DF2 and PBE0-TS methods estimate the dispersion energies from the calculated electron density. In these approximations, the interaction energies around the equilibrium point are reasonably close to the CCSD(T) results but sometimes slightly deviate from them because interaction energies were not particularly optimized with parameters. Nevertheless, because the electron cloud deforms when neighboring atoms/ions induce an electric field, both vdW-DF2 and PBE0-TS seem to properly reproduce the resulting change of dispersion interaction. Thus, improvements are needed in both vdW-DF2 and PBE0-TS to better describe the interaction energies, while the B97-D3 method could benefit from the incorporation of polarization-driven energy changes that show highly anisotropic behavior. Although the current DFT-D methods need further improvement, DFT-D is very useful for computer-aided molecular design. We have used these newly developed DFT-D methods to calculate the interactions between graphene and DNA nucleobases. Using DFT-D, we describe the design of molecular receptors of π-systems, graphene based electronic devices, metalloporphyrin half-metal based spintronic devices as graphene nanoribbon (GNR) analogs, and graphene based molecular electronic devices for DNA sequencing. DFT-D has also helped us understand quantum phenomena in materials and devices of π-systems including graphene.

Enhancement of interlayer exchange coupling via intercalation in 2D magnetic bilayers: towards high Curie temperature.

Two-dimensional magnetic materials are considered as promising candidates for developing next-generation spintronic devices by providing the possibility of scaling down to nanometers. However, a low Curie temperature is a crucial problem for practical applications, being intimately related to weak interlayer exchange coupling. Here, by using density functional theory calculations, we show that interlayer exchange coupling can be enhanced by intercalating 3d transition metals (Sc to Zn) into a bilayer of CrI3 and NiI2. It is found that intercalated Ni and Cr atoms exhibit strong antiferromagnetic coupling with the CrI3 and NiI2 host layers, respectively. This enhances the ferromagnetic interlayer exchange coupling between the host layers by many folds compared to pristine CrI3 and NiI2 bilayers. Moreover, both intercalated compounds show out-of-plane magnetic anisotropy with half metallic nature, which makes them ideal candidates for spintronics applications. Thereby our work provides a rational approach to raise the Curie temperature of non-metallic two-dimensional magnets by intercalation.

Single-atom catalysts supported on a hybrid structure of boron nitride/graphene for efficient nitrogen fixation via synergistic interfacial interactions.

Hexagonal boron nitride (BN) shows significant chemical stability and promising thermal nitrogen reduction reaction (NRR) activity but suffers from low conductivity in electrolysis with a wide band gap. To overcome this problem, two-dimensional (2D) BN and graphene (G) are designed as a heterostructure, namely BN/G. According to density functional theory (DFT), the higher conductivity of G narrows the band gap of BN by inducing some electronic states near the Fermi energy level (Ef). Once transition metals (TMs) are anchored in the BN/G structure as single atom catalysts (SACs), the NRR activity improves as the inert BN basal layer activates with moderate *NH2 binding energy and further the band gap is reduced to zero. V (vanadium) and W (tungsten) SACs exhibit the best performance with limiting potentials of -0.22 and -0.41 V, respectively. This study helps in understanding the improvement of the NRR activity of BN, providing physical insights into the adsorbate-TM interaction.

Agri-waste derived electroactive carbon-iron oxide nanocomposite for oxygen reduction reaction: an experimental and theoretical study.

Herein, we have utilized agri-waste and amalgamating low Fe3+, to develop an economic iron oxide-carbon hybrid-based electrocatalyst for oxygen reduction reaction (ORR) with water as a main product following close to 4e- transfer process. The electrocatalytic activity is justified by electrochemical active surface area, synergetic effect, and density functional theory calculations.

Orbital selective Fermi surface shifts and mechanism of high T(c) superconductivity in correlated AFeAs (A=Li, Na).

Based on the dynamical mean field theory and angle resolved photoemission spectroscopy, we have investigated the mechanism of high T(c) superconductivity in stoichiometric LiFeAs. The calculated spectrum is in excellent agreement with the measured angle resolved photoemission spectroscopy. The Fermi surface (FS) nesting, which is predicted in the conventional density functional theory method, is suppressed due to the orbital-dependent correlation effect within the dynamical mean field theory method. We have shown that such marginal breakdown of the FS nesting is an essential condition to the spin-fluctuation mediated superconductivity, while the good FS nesting in NaFeAs induces a spin density wave ground state. Our results indicate that a fully charge self-consistent description of the correlation effect is crucial in the description of the FS nesting-driven instabilities.

Impact of fluorination on the energy level alignment of an F n ZnPc/MAPbI3 interface.

We have studied interactions at an interface between a Methylammonium Lead Iodide (MAPbI3) surface and zinc-phthalocyanine molecules with F substituting peripheral H (F n ZnPc; n = 4, 8, 12, and 16) by employing hybrid density functional theory (DFT) based simulations. These calculations show that F n ZnPc molecules form a stable interface with MAPbI3, whose binding strength is comparable to that of the un-substituted (ZnPc) case. As a consequence of fluorination, an increase in the ionization potential/electron affinity (i.e., a systematic lowering of molecular energy levels), as well as interfacial charge transfer, is observed whose magnitude depends upon the degree of fluorination. In contrast to the common belief of unfavorable hole transfer for excessive fluorination, our work unveils that the valence band offset remains favorable for all ranges of substitution (n); thus, hole transfer from MAPbI3 to F n ZnPc is facilitated while the electron transfer process is suppressed. This unusual behavior originates from the intermolecular interaction and substrate-to-molecule electron transfer at the heterojunction, which gradually suppresses the downward shift of F n ZnPc energy levels by increasing the value of n. Given the beneficial impacts of fluorination, such as hydrophobicity, our work provides valuable insight for exploiting stable F n ZnPc towards high-efficiency perovskite solar cells.

Unveiling the Role of Charge Transfer in Enhanced Electrochemical Nitrogen Fixation at Single-Atom Catalysts on BX Sheets (X = As, P, Sb).

To tune single-atom catalysts (SACs) for effective nitrogen reduction reaction (NRR), we investigate various transition metals implanted on boron-arsenide (BAs), boron-phosphide (BP), and boron-antimony (BSb) using density functional theory (DFT). Interestingly, W-BAs shows high catalytic activity and excellent selectivity with an insignificant barrier of only 0.05 eV along the distal pathway and a surmountable kinetic barrier of 0.34 eV. The W-BSb and Mo-BSb exhibit high performances with limiting potentials of -0.19 and -0.34 V. The Bader-charge descriptor reveals that the charge transfers from substrate to *NNH in the first protonation step and from *NH3 to substrate in the last protonation step, circumventing a big hurdle in NRR by achieving negative free energy change of *NH2 to *NH3. Furthermore, machine learning (ML) descriptors are introduced to reduce computational cost. Our rational design meets the three critical prerequisites of chemisorbing N2 molecules, stabilizing *NNH, and destabilizing *NH2 adsorbates for high-efficiency NRR.

Conformational heterogeneity of molecules physisorbed on a gold surface at room temperature.

A quantitative single-molecule tip-enhanced Raman spectroscopy (TERS) study at room temperature remained a challenge due to the rapid structural dynamics of molecules exposed to air. Here, we demonstrate the hyperspectral TERS imaging of single or a few brilliant cresyl blue (BCB) molecules at room temperature, along with quantitative spectral analyses. Robust chemical imaging is enabled by the freeze-frame approach using a thin Al2O3 capping layer, which suppresses spectral diffusions and inhibits chemical reactions and contamination in air. For the molecules resolved spatially in the TERS image, a clear Raman peak variation up to 7.5 cm-1 is observed, which cannot be found in molecular ensembles. From density functional theory-based quantitative analyses of the varied TERS peaks, we reveal the conformational heterogeneity at the single-molecule level. This work provides a facile way to investigate the single-molecule properties in interacting media, expanding the scope of single-molecule vibrational spectroscopy studies.

The impact of molecular orientation on carrier transfer characteristics at a phthalocyanine and halide perovskite interface.

We have studied the interface properties of metal phthalocyanine (MPc, M = Zn, Cu) molecules at a methylammonium lead iodide (MAPbI3) surface using density functional theory (DFT) based simulations. From the adsorption energies, the face-on orientation is found to have an order of magnitude stronger binding energy than the edge-on orientation, where CuPc binds a little stronger than ZnPc with its closer interfacial distance. Our detailed analysis of interface electronic structure suggests that the edge-on configuration possesses a large energy barrier for the hole transfer from MAPbI3 to MPc molecules. In contrast, the face-on configuration has no such barrier, facilitating the hole transfer, while at the same time the desirable alignment of the conduction band suppresses the electron-hole recombination. Therefore, the face-on configuration is clearly found to be more suitable for the photovoltaic process, in line with the experimental reports. Our work emphasizes the impact of MPc orientation upon perovskite solar cell efficiency besides other factors such as Pc thin film's mobility and morphology, and provides insightful guidance to efficient and stable hole transport layers.

Facile room-temperature self-assembly of extended cation-free guanine-quartet network on Mo-doped Au(111) surface.

Guanine-quadruplex, consisting of several stacked guanine-quartets (GQs), has emerged as an important category of novel molecular targets with applications from nanoelectronic devices to anticancer drugs. Incorporation of metal cations into a GQ structure is utilized to form stable G-quadruplexes, while formation of a cation-free GQ network has been challenging. Here we report the room temperature (RT) molecular self-assembly of extended pristine GQ networks on an Au(111) surface. An implanted molybdenum atom within the Au(111) surface is used to nucleate and stabilize the cation-free GQ network. Additionally, decoration of the Au(111) surface with 7-armchair graphene nanoribbons (7-AGNRs) enhances the GQ domain size by suppressing the influence of the disordered phase nucleated from Au step edges. Scanning tunneling microscopy/spectroscopy (STM/STS) and density functional theory (DFT) calculations confirm the formation of GQ networks and unravel the nucleation and growth mechanism. Our work, utilizing a hetero-atom doped substrate, provides a facile approach to enhance the stability and domain size of the GQ self-assembly, which would be applicable for other molecular structures.