Density Functional Model Research Articles

Efficient attosecond pulse generation from WS2 semiconductor by tailoring the driving laser pulse

High harmonic generation in semiconductor materials with ultra-short pulses of the femtosecond order provides a promising approach to generate attosecond pulses and control the electron dynamics. In this study, an accurate time dependent density functional theory model describing high-order harmonic generation in WS2 bulk is investigated. The effect of driving laser specifications such as ellipticity and chirp rate on producing attosecond pulse is studied. The results show that using a nonlinearly chirped laser can lead to generation of harmonics up to 50 eV, and consequently, production of an attosecond pulse with duration of 440 as. Moreover, a two-color chirped driving laser is proposed which is capable of increasing harmonics up to 63 eV with a slight decrease in the intensity, and reducing the output attosecond pulse duration to 310 as. Our results offer a valuable route towards development of solid-state high harmonic generation spectroscopy and high-performance attosecond source applications.

Two Steps to Bicyclo[4.2.0]octadienes from Cyclooctatetraene: Total Synthesis of Kingianic Acid A.

Synthetic approaches to bicyclo[4.2.0]octadiene natural products frequently employ the synthesis of linear tetraenes to initiate a biosynthetic 8π/6π-electrocyclization cascade. This work forges a functionalized bicyclo[4.2.0]octadiene in two steps from cyclooctatetraene. The versatility of this method is demonstrated through natural product synthesis, including the first total synthesis of kingianic acid A and formal syntheses of kingianins A, D, and F and cryptobeilic acid D ethyl ester. The unexpected formation of an E,E,Z,E-tetraene byproduct is rationalized through density functional theory modeling.

Solving the Puzzle of Unusual Excited-State Proton Transfer in 2,5-Bis(6-methyl-2-benzoxazolyl)phenol.

2,5-Bis(6-methyl-2-benzoxazolyl)phenol (BMP) exhibits an ultrafast excited-state intramolecular proton transfer (ESIPT) when isolated in supersonic jets, whereas in condensed phases the phototautomerization is orders of magnitude slower. This unusual situation leads to nontypical photophysical characteristics: dual fluorescence is observed for BMP in solution, whereas only a single emission, originating from the phototautomer, is detected for the ultracold isolated molecules. In order to understand the completely different behavior in the two regimes, detailed photophysical studies have been carried out. Kinetic and thermodynamic parameters of ESIPT were determined from stationary and transient picosecond absorption and emission for BMP in different solvents in a broad temperature range. These studies were combined with time-dependent- density functional theory quantum-chemical modeling. The excited-state double-well potential for BMP and its methyl-free analogue were calculated by applying different hybrid functionals and compared with the results obtained for another proton-transferring molecule, 2,5-bis(5-ethyl-2-benzoxazolyl)hydroquinone (DE-BBHQ). The results lead to the model that explains the difference in proton-transfer properties of BMP in vacuum and in the condensed phase by inversion of the two lowest singlet states occurring along the PT coordinate.

CDFTPY: A python package for performing classical density functional theory calculations for molecular liquids

Classical density functional theory (CDFT) provides a rigorous theoretical framework for the statistical mechanics based analysis of many-body systems. This approach has proven to be successful in simulations of mono-atomic, i.e. simple liquids, and there is an ongoing theoretical effort in extending it to more complex polyatomic, molecular liquid systems. Sharing these developments in the form of open-source and easily accessible codes could greatly benefit these efforts. In this work, we present python-based CDFT code that contains both conventional Reference Interaction Site Model (RISM) and recently developed renormalized site density theory (RSDFT) approach. The current implementation is focused on ion solvation - the problem of both fundamental and practical importance. It allows the calculation of individual ions as well as comparative analysis across a range of interaction parameters. Program summaryProgram Title: cdftpyCPC Library link to program files:https://doi.org/10.17632/p8dsgz5n4g.1Developer's repository link:https://github.com/opencdftLicensing provisions: GPLv3Programming language: python 3.9+Nature of problem: Computational modeling of molecular liquids at the atomistic level of resolution is an important capability across many scientific areas. Classical density functional theory (CDFT) approaches this problem by building statistical mechanics model of the system in terms of its average atomic (site) density. Such an approach can provide orders of magnitudes improvements in efficiency compared to conventional molecular dynamics simulations, but requires special treatment of multi-scale interactions in a molecular liquid. A practical utility of our open-source python based implementation of CDFT is the study the problem solvation of ions or Lennard-Jones particles.Solution method: Python package developed in this work provides two CDFT implementations for molecular liquids - renormalized site density functional theory and reference interaction site model. It enables calculations of thermodynamic and structural properties related to solvation of spherical solutes. The nonlinear integral equations associated with the two methods are solved iteratively, utilizing Fast Fourier Transform (FFT) for the calculation of the numerically intensive convolution integrals. The resulting code provides near instantaneous evaluation of the solvated properties of individual solutes and high-throughput screening across the range of different solute parameters.

Explaining the structure sensitivity of Pt and Rh for aqueous-phase hydrogenation of phenol.

Phenol is an important model compound to understand the thermocatalytic (TCH) and electrocatalytic hydrogenation (ECH) of biomass to biofuels. Although Pt and Rh are among the most studied catalysts for aqueous-phase phenol hydrogenation, the reason why certain facets are active for ECH and TCH is not fully understood. Herein, we identify the active facet of Pt and Rh catalysts for aqueous-phase hydrogenation of phenol and explain the origin of the size-dependent activity trends of Pt and Rh nanoparticles. Phenol adsorption energies extracted on the active sites of Pt and Rh nanoparticles on carbon by fitting kinetic data show that the active sites adsorb phenol weakly. We predict that the turnover frequencies (TOFs) for the hydrogenation of phenol to cyclohexanone on Pt(111) and Rh(111) terraces are higher than those on (221) stepped facets based on density functional theory modeling and mean-field microkinetic simulations. The higher activities of the (111) terraces are due to lower activation energies and weaker phenol adsorption, preventing high coverages of phenol from inhibiting hydrogen adsorption. We measure that the TOF for ECH of phenol increases as the Rh nanoparticle diameter increases from 2 to 10nm at 298K and -0.1V vs the reversible hydrogen electrode, qualitatively matching prior reports for Pt nanoparticles. The increase in experimental TOFs as Pt and Rh nanoparticle diameters increase is due to a larger fraction of terraces on larger particles. These findings clarify the structure sensitivity and active site of Pt and Rh for the hydrogenation of phenol and will inform the catalyst design for the hydrogenation of bio-oils.

Adsorption of Oxygen to High Entropy Alloy Surfaces for up to 2 ML Coverage Using Density Functional Theory and Monte Carlo Calculations

High-entropy alloys (HEAs) manufactured with refractory elements are candidates for high-temperature structural applications. To enhance our understanding of oxidation in these complex systems, the early stages of oxidation on the surface of Al10Nb15Ta5Ti30Zr40 were studied using density functional theory and thermodynamic modeling. Surface slabs were generated from bulk configurations sampled from equilibrium using a multicell Monte Carlo method for phase prediction. The bulk structure was found to be a single BCC phase in good agreement with experimental observations. The oxygen adsorbed with a strong preference for sites with Ti and Zr and avoided sites with Nb-Al and Nb-Ta. The surface was shown to be highly reactive to oxygen, yielding a dominating oxygen coverage of two monolayers over the temperature range of 100 to 2600 K and an oxygen pressure range of 10-30 to 105 bar. Recovering a clean surface slab was not achieved until pressures approached vacuum conditions and temperature exceeded 1900 K, demonstrating the difficulty of oxygen removal from the surface. Grand canonical Monte Carlo simulations showed that high Nb content in the top surface layer reduced the surface reactivity to incoming oxygen. Inward oxygen diffusion at low coverage was preferred in regions rich with Zr but slowed with the addition of Ti and Al. Diffusion rates drastically decreased at 1 ML, especially in the region rich with Ti and Zr, where strong metal-oxygen bonds were reported. Our results indicated that a high content of Ti and Zr increased the reactivity of the HEA surface to oxygen. The presence of Nb also enhanced the resistance to oxygen adsorption, especially when partnered with Al and Ta. Inward oxygen diffusion was likely to occur at low coverage in regions rich with Zr but could be protected against with the addition of Al and Ti. The limitations of the present work are discussed. This study may provide insights that assist with devising short- and long-term mitigation strategies against material degradation related to high-temperature oxidation.

Experimental and density functional theoretical modeling of triazole pesticides extraction by Ti2C nanosheets as a sorbent in dispersive solid phase extraction method before HPLC-MS/MS analysis

In this research, a convenient, fast, and green dispersive solid phase extraction procedure based on Ti2C nanosheets was developed for effectively enrichment of some triazole pesticides prior to high performance liquid chromatography-tandem mass spectrometry. Characterization of the etching sorbent was carried out in details. Adsorption and desorption steps have been optimized in detail to obtain efficient phase separation and reliable analytical results. Under optimized conditions, the presented method exhibited a wide working range (0.52–1000 ng mL−1), low detection limits (0.03–0.30 ng mL−1) and acceptable extraction recoveries (70–75%). The introduced method precision was checked by calculating intra and inter-day relative standard deviations for three different concentrations of triazole pesticides. The matrix effect was investigated by the recovery study. Following validation studies, the presented method was successfully applied to the extraction and determination of the studied triazole pesticides from fruit juice samples. The adsorption mechanism was supported by theoretical studies. The interactions between the studied pesticides and Ti2C nanosheets were investigated with the help of density functional theoretical calculations. The calculations supported the obtained experimental results.

Surface pourbaix plots of M@N4-graphene single-atom electrocatalysts from density functional theory thermodynamic modeling

Single-atom catalysts (SACs) are rapidly developing in various application areas, including electrocatalysis of different reactions, usually taking place under harsh pH/electrode potential conditions. Thus, a full atomic-level understanding of the nature of the active sites under realistic electrochemical conditions is needed, having in mind that the state of SACs active centers could be altered by the adsorption of spectating species. In this contribution, Density Functional Theory is employed to conduct thermodynamic analysis of SACs with metal atoms (Mn, Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, Ir, Pt, or Au) embedded into N4 moiety in graphene. Various surface electrochemical processes on such SACs are considered, their Pourbaix plots are constructed, and their activity, selectivity, and stability under operating conditions are discussed. It is demonstrated how adsorption of H, O and OH can cause blockage and restructuring of the active sites and alter the electronic structure. Furthermore, when one deals with metals with lower d-band filling, it is shown that metal center oxidation is preferred over the oxidation of carbon lattice. The effect of the state of the metal center on the reactivity of the carbon lattice is discussed in the case of Fe@N4-graphene. Finally, a possible strategy for confirming the changes in the architecture of the SACs’ active site by analyzing their vibration spectra is suggested.

Guiding Graphene Derivatization for the On‐Chip Multisensor Arrays: From the Synthesis to the Theoretical Background

AbstractEngineering the physics and chemistry of 2D materials is a key to unlock the potential of the advanced e‐nose technologies limited by the current semiconductor technologies. Herein, the adjustment of the graphene's morphology, physics, and gas sensing properties upon its carboxylation via the developed photochemical method is demonstrated. Formation of matrices of nanoscale holes yet with the retention of the lamellar structure of the graphene layer is signified upon the introduction of up to 9.5 at% of carboxyl groups. The impact of the applied carboxylation on the conduction mechanism and electronic structure is demonstrated. The appearance of a set of the localized states in the valence band is revealed, originating from the molecular orbitals of carboxyls as is signified by the proposed approach for the identification of electronic states in graphene chemical derivatives. Given holey structure, predominance of highly affine carboxyls, and lateral inhomogeneity, the enhanced detection and discrimination of various alcohols, acetone, and ammonia vapors at room temperature is demonstrated. The opposite chemiresistive response toward ammonia in the humid air is also experimentally revealed and justified by the performed density functional theory modeling on the effect of ammonia, water, and their mix on electronic structure, and resistivity of the carboxylated graphene.

Dissolving Diamond: Kinetics of the Dissolution of (100) and (110) Single Crystals in Nickel and Cobalt Films

We report a study of the kinetics of dissolution of (100) and (110) single-crystal diamond plates (“D(100)” and “D(110)”) in thin films of nickel (Ni) and cobalt (Co). This dissolution occurs at the metal–D(100) or metal–D(110) interface and was studied in the presence and also in the absence of water vapor at temperatures near 1000 °C. The single-crystal D(100) dissolves in Ni, and also in Co, in the temperature range 900–1050 °C. The dissolution is too slow to measure below 900 °C. In an argon (Ar) atmosphere (under an Ar(g) flow at 1000 sccm and 1 atm pressure, with no water vapor present in the reaction chamber) and at any temperature in the range 900–1050 °C, the metal film is rapidly saturated with dissolved carbon (C), thin graphite films form on the free metal surface and at the metal–D interface during heating at or above 650 °C, and the dissolution of the diamond then stops. For addition of water vapor, its partial pressure was controlled by using a water bubbler immersed in a constant temperature bath and Ar(g) was used as the carrier gas. We discovered two different regimes (I and II) for the kinetics of dissolution of D(100) and D(110), in which the rate-determining step was the removal of carbon atoms on the open metal surface (regime I, lower partial pressure of water vapor) or dissolution of diamond at the metal–diamond interface (regime II, higher partial pressure of water vapor) that yielded different Arrhenius parameters. Time-of-flight-secondary ion mass spectrometry depth profiles show the concentration gradient of C from a certain depth into the metal film surface down to the M–D(100) interface, and residual gas analyzer measurements show that the gas products formed in the presence of water vapor on the metal surface are CO and H2. It was found that the rate of dissolution of diamond in Co was higher than that in Ni for both D(100) and D(110) and for both regimes I and II, and possible reasons are suggested. We also found that D(111) could not be dissolved at the Ni/D(111) and Co/D(111) interface in the presence of water vapor (over the same range of sample temperatures). The reaction paths for dissolution of C at the M–D(100) or M–D(110) interface and for removal of C from the free surfaces of Ni and Co were assessed through density functional theory modeling at 1273 K.

Generalizing the Inequality Process’ gamma model of particle wealth statistics

ABSTRACT The Inequality Process (IP) has been tested and confirmed against data on incomes that are approximately gamma distributed. The IP’s gamma pdf (probability density function) model expresses statistics of IP particle wealth algebraically in terms of IP parameters for the subset of IP parameters that generate approximately gamma distributions of particle wealth, a serious limitation, one leaving statistics of the many empirical distributions of income and wealth with heavier-than-gamma distribution right tails beyond algebraic expression in terms of IP particle parameters. This paper shows that an IP variance-gamma (VG) pdf model can do for the entire interval on which IP particle parameters are defined, (0,1), what the IP’s gamma pdf model does for only a subset. This paper thus generalizes the IP’s gamma pdf model, and it does so with no loss of parsimony since the IP’s VG pdf model is, like the IP’s gamma pdf model, expressed in terms of IP particle parameters.

Ultrastable Porous Covalent Organic Framework Assembled Carbon Nanotube as a Novel Nanocontainer for Anti-Corrosion Coatings: Experimental and Computational Studies.

Covalent organic frameworks (COFs) have been proposed as a wholly organic architecture sharing high crystallinity, porosity, and tuneability. Moreover, they exhibit highly stable structures against harsh chemical environments, including boiling water, strong acids and bases, and oxidation and reduction conditions, making them good candidates for extreme conditions. For the first time, a porous COF structure based on terephthalaldehyde and melamine was synthesized and employed as a novel nanocontainer for hosting corrosion inhibitors to provide a coating with superior active/passive anti-corrosion properties. In this study, the multi-walled carbon nanotube was utilized as a platform for growing COF (CC) to improve the coating's barrier and thermo-mechanical properties. The zinc cations were loaded into the CC structure (called CCZ) as one of the most promising inhibitors for mild steel. The COF-based nanoparticles' characterization was done by Fourier transform infrared, Raman, X-ray diffraction, thermogravimetric analysis, Brunauer-Emmett-Teller, field emission scanning electron microscopy, and transmission electron microscopy (TEM) techniques. Moreover, the Density functional theory modeling and molecular dynamics simulation quantitatively highlighted the adsorption propensity of the investigated COF structures onto the oxidized CNT-based nanostructures and the interactions of epoxy with these nanostructures. The CCZ nanoparticles (NPs) showed 75% inhibition efficiency in saline solution and 418 ppm zinc ions release after 24 h at acidic pH. The CCZ/EP coating revealed the smart release of inhibitor for 24 h and represented excellent barrier properties after 9 weeks of immersion in saline solution. In terms of mechanical properties, the elastic modulus values derived from the dynamic mechanical thermal analyzer were enhanced by 107 and 137% in CC/EP and CCZ/EP samples compared to the neat epoxy. Furthermore, the yield stress and breakpoint elongation were strengthened by 102 and 63% for the CC/EP sample, respectively. Finally, the highest pull-off adhesion strength in dry (8.53 MPa) and wet (2.7 MPa) conditions, along with the lowest adhesion loss (68.3%), was related to the CCZ/EP sample.

Spatially resolved fluorescence of caesium lead halide perovskite supercrystals reveals quasi-atomic behavior of nanocrystals

We correlate spatially resolved fluorescence (-lifetime) measurements with X-ray nanodiffraction to reveal surface defects in supercrystals of self-assembled cesium lead halide perovskite nanocrystals and study their effect on the fluorescence properties. Upon comparison with density functional modeling, we show that a loss in structural coherence, an increasing atomic misalignment between adjacent nanocrystals, and growing compressive strain near the surface of the supercrystal are responsible for the observed fluorescence blueshift and decreased fluorescence lifetimes. Such surface defect-related optical properties extend the frequently assumed analogy between atoms and nanocrystals as so-called quasi-atoms. Our results emphasize the importance of minimizing strain during the self-assembly of perovskite nanocrystals into supercrystals for lighting application such as superfluorescent emitters.

The possibility of Eriochrome black T dye removal from wastewater by using BC3 nanotube; quantum chemical study

Herein, we aim to investigate the structure, intermolecular forces, electronic features, and durability in a solution of complexes formed between Eriochrome black T dye (EBT) and BC3 nanotube (BC3NT) by density functional theory modeling. Possible applications for the removal of EBT were studied with the help of BC3NT. The energy of adsorption is about −36.76 kcal/mol for the interaction between EBT and a boron atom of the tube via its O atom. The electrical features of BC3NT are significantly affected by EBT, making them appropriate for the adsorption process. Also, donor–acceptor interaction mainly controlled the adsorption mechanism of EBT. This work, on the one hand, boosts the enhancement of low-cost and tolerable heteroatom carbon-based materials. On the other hand, it systematically investigates the mechanism of adsorption heteroatom carbonaceous structures for EBT.

Numerical simulation of combustion of sulfide- biomass concentrate ingredients and contaminants in copper furnace smelting

Co-firing biomass and fossil fuels in industrial furnaces is a suitable way to reduce the environmental impact of human activities with acceptable investment. In this paper, the results of numerical simulation co-firing of sulfide concentrate and three auxiliary fuels, including gasoil, kerosene, and sawdust biomass, are compared in the flash furnace copper smelting. For modeling of turbulent flow and combustion, RNG, k-ε model, and probability density function model (pdf) have been used, respectively. This study has been carried out to investigate the furnace temperature and combustion pollutants distribution. The numerical simulation results show that the flame temperature resulting from the combustion of diesel fuel and sawdust as auxiliary fuel is the highest and lowest, respectively. In biomass combustion, despite that the flame temperature is low, but the NOx mass fraction increases because there is nitrogen in the sawdust chemical composition. Also in sawdust combustion, the oxygen content is high, the SO2 and SO3 sulfur pollutants increase in the high temperatures regions of the furnace and the lower temperature of the auxiliary fuel burner, respectively. Because SO2 is formed at high temperatures (> 1273K), oxygen-rich and SO3 species are produced at relatively low temperatures with excess oxygen. The amount of CO emissions in sawdust combustion is much lower than the amount of combustion of diesel and oil. In the peak of the flash furnace for sawdust and diesel auxiliary fuels, the temperature is 2.29E+03 K, and the distribution of NOx, CO2, O2, SO2, and SO3 are 1.51E-04, 9.72E-02, 2.33E-03, 1.71E-01 and 2.45E-02 respectively.

Inclusive electron scattering in the quasielastic region with the Korea-IBS-Daegu-SKKU density functional

With the framework of KIDS (Korea-IBS-Daegu-SKKU) density functional model, the isoscalar and isovector effective masses of nucleon and the effect of symmetry energy in nuclear medium are investigated in inclusive $(e,e')$ reaction in quasielastic region. The effective masses are varied in the range $(0.7 \sim 1.0)M$ with free nucleon mass $M$, and the symmetry energy is varied within the uncertainty allowed by nuclear data and neutron star observation. The wave functions of nucleons inside target nucleus are generated by solving Hartree-Fock equation with adjusting equation of state, binding energy and radius of various stable nuclei, and effective mass of nucleon in the KIDS model. With the obtained wave functions, we calculate the differential cross section for the inclusive $(e,e')$ reaction and compare the theoretical results with Bates, Saclay, and SLAC experimental data. Our model describes experimental data better at SLAC-type high incident electron energy than those measured from Bates and Saclay. The influence of the effective mass and symmetry energy appears to be precise on the longitudinal cross section.

Configurational entropy from a replica approach: A density-functional model.

We study a field-theoretic model for the metastable liquid using a nonlocal free-energy functional with density ρ(x) is the order parameter and three-point correlation effects included in the formulation. We assume fragmentation of the free-energy landscape into distinct basins of local minima and evaluate the partition function for the many-particle system through mapping into a composite system of m identical replicas. Static correlations and configurational entropy S_{c} are calculated in the m=1 limit. The Kauzman packing fraction η_{K} obtained are in agreement with other works.

Topological viewpoint of two-dimensional group III–V and IV–IV compounds in the presence of electric field and spin–orbit coupling by density functional theory and tight-binding model

Using the tight-binding (TB) model and density functional theory, the topological invariant of the two-dimensional (2D) group III–V and IV–IV compounds are studied in the absence and the presence of an external perpendicular electric field and spin–orbit coupling. It will be recognized that a critical value of these parameters changes the topological invariant of 2D graphene-like compounds. The significant effects of an external electric field and spin–orbit coupling are considered to the two-center overlap integrals of the Slater–Koster model involved in band structures, changing band-gap, and tuning the topological phase transition between ordinary and quantum spin Hall regime. These declare the good consistency between two theories: TB and density functional. So, this study reveals topological phase transition in these materials. Our finding paves a way to extend an effective Hamiltonian, and may instantly clear some computation aspects of the study in the field of spintronic based on the first-principles methods.

Assessment of Finite-Rate Chemistry Effects in a Turbulent Dilute Ethanol Spray Flame

Simulations of a benchmark ethanol dilute spray flame are performed with four combustion models at different levels of closure for turbulence–chemistry interaction (TCI) to provide a head-to-head comparative analysis on the closure effects of TCI. The evaluation is performed in the context of Reynolds-averaged Navier–Stokes simulations taking advantage of the simple jet configuration, together with a Lagrangian discrete phase model for tracking the spray droplets. Two well-validated ethanol mechanisms consisting of 40 and 50 species, respectively, are employed to describe the chemical kinetics and reveal the impact of chemistry. Results are compared against measurement, including gas-phase velocity, temperature, and droplet velocity, demonstrating the improvement with the increasing accuracy in TCI modeling from characteristic time scale model, laminar finite rate model, eddy dissipation concept model, and transported probability density function (PDF) model. Effects of micromixing in PDF simulation are further investigated considering different model formulations and mechanical-to-scalar timescale ratios (). The Euclidean minimum spanning tree model with yields the best prediction of the mean temperature. The analysis on flame structure suggests that the flame exhibits a mixed mode of combustion, i.e., a stratified premixed flame in the upstream and a typical non-premixed flame in the downstream.

A first principles study of the adsorption and hydrogenation of formic acid on a Cu3Zn material: Implication for bulk alloying effect on CO2 hydrogenation reactivity of Cu/ZnO-based catalysts

HCOOH hydrogenation to H2COOH were, until recently, assumed to be the rate controlling step in methanol synthesis from CO2/H2 mixtures over Cu-based catalysts. Using the density functional method and periodic supercell slab models, we have studied the critical elementary reaction, along with the molecular adsorption of HCOOH, on the clean, H, CH3O, and H + CH3O-precovered Cu3Zn(114), Cu3Zn(214) and, as a reference, Cu(111) substrates, which are intimately related to the surface chemical composition of real CO2 hydrogenation catalysts. Among the three metal and alloyed surfaces with and without coadsorbates, the stepped alloy surface is always the optimum site for HCOOH binding, thereby serving as a reservoir for the reactive HCOOH species. And the atomically flat alloy surface shows more favorable kinetics and thermochemistry than the pure copper substrate for H2COOH formation. The synergetic interaction between the alloyed surfaces in promoting the slow reaction reveals that a binary bulk alloy, while present in reduced Cu/ZnO catalyst, demonstrates promising catalytic performance in terms of activity towards the overall methanol synthesis process. This paper stresses that there is a requirement for further experimental validation studies.