Cation doping and oxygen vacancies in the orthorhombic FeNbO4 material for solid oxide fuel cell applications: A density functional theory study.

The orthorhombic phase of FeNbO4, a promising anode material for solid oxide fuel cells (SOFCs), exhibits good catalytic activity toward hydrogen oxidation. However, the low electronic conductivity of the material specifically in the pure structure without defects or dopants limits its practical applications as an SOFC anode. In this study, we have employed density functional theory (DFT + U) calculations to explore the bulk and electronic properties of two types of doped structures, Fe0.9375A0.0625NbO4 and FeNb0.9375B0.0625O4 (A, B = Ti, V, Cr, Mn, Co, Ni) and the oxygen-deficient structures Fe0.9375A0.0625NbO3.9375 and FeNb0.9375B0.0625O3.9375, where the dopant is positioned in the first nearest neighbor site to the oxygen vacancy. Our DFT simulations have revealed that doping in the Fe sites is energetically favorable compared to doping in the Nb site, resulting in significant volume expansion. The doping process generally requires less energy when the O-vacancy is surrounded by one Fe and two Nb ions. The simulated projected density of states of the oxygen-deficient structures indicates that doping in the Fe site, particularly with Ti and V, considerably narrows the bandgap to ∼0.5 eV, whereas doping with Co at the Nb sites generates acceptor levels close to 0 eV. Both doping schemes, therefore, enhance electron conduction during SOFC operation.

Exploring the Redox Properties of the Low-Miller Index Surfaces of Copper Tungstate (CuWO4): Evaluating the Impact of the Environmental Conditions on the Water Splitting and Carbon Dioxide Reduction Processes.

Photocatalysis has gained significant attention and interest as an environmentally friendly and sustainable approach to the production of hydrogen through water splitting and the reduction and conversion of CO2. Copper tungstate (CuWO4) is a highly promising candidate for these applications owing to its appropriate bandgap and superior stability under different conditions. However, the redox behavior of the CuWO4 surfaces under different environments and their impact on the morphology of the material nanoparticles, as well as the electronic properties, remain poorly understood. In this study, we have employed density functional theory calculations to investigate the properties of the bulk and pristine surfaces of CuWO4 and how the latter are impacted by oxygen chemisorption under the conditions required for photocatalytic water splitting and carbon dioxide reduction processes. We have calculated the lattice parameters and electronic properties of the bulk phase, as well as the surface energies of all possible nonpolar, stoichiometric, and symmetric terminations of the seven low-Miller index surfaces and found that the (010) and (110) facets are the thermodynamically most stable. The surface-phase diagrams were used to derive the equilibrium crystal morphologies, which show that the pristine (010) surface is prominent under synthesis and room conditions. Our crystal morphologies suggest that the partially oxidized (110) surface and the partially reduced (011) surface may play an important role in the photocatalytic splitting of water and CO2 conversion, respectively. Our results provide a comprehensive understanding of the CuWO4 surfaces under the conditions of important photocatalytic applications.

Development of 2-in-1 Sensors for the Safety Assessment of Lithium-Ion Batteries via Early Detection of Vapors Produced by Electrolyte Solvents.

Batteries play a critical role in achieving zero-emission goals and in the transition toward a more circular economy. Ensuring battery safety is a top priority for manufacturers and consumers alike, and hence is an active topic of research. Metal-oxide nanostructures have unique properties that make them highly promising for gas sensing in battery safety applications. In this study, we investigate the gas-sensing capabilities of semiconducting metal oxides for detecting vapors produced by common battery components, such as solvents, salts, or their degassing products. Our main objective is to develop sensors capable of early detection of common vapors produced by malfunctioning batteries to prevent explosions and further safety hazards. Typical electrolyte components and degassing products for the Li-ion, Li-S, or solid-state batteries that were investigated in this study include 1,3-dioxololane (C3H6O2─DOL), 1,2-dimethoxyethane (C4H10O2─DME), ethylene carbonate (C3H4O3─EC), dimethyl carbonate (C4H10O2─DMC), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium nitrate (LiNO3) salts in a mixture of DOL and DME, lithium hexafluorophosphate (LiPF6), nitrogen dioxide (NO2), and phosphorous pentafluoride (PF5). Our sensing platform was based on ternary and binary heterostructures consisting of TiO2(111)/CuO(1̅11)/Cu2O(111) and CuO(1̅11)/Cu2O(111), respectively, with various CuO layer thicknesses (10, 30, and 50 nm). We have analyzed these structures using scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), micro-Raman spectroscopy, and ultraviolet-visible (UV-vis) spectroscopy. We found that the sensors reliably detected DME C4H10O2 vapors up to a concentration of 1000 ppm with a gas response of 136%, and concentrations as low as 1, 5, and 10 ppm with response values of approximately 7, 23, and 30%, respectively. Our devices can serve as 2-in-1 sensors, functioning as a temperature sensor at low operating temperatures and as a gas sensor at temperatures above 200 °C. Density functional theory calculations were also employed to study the adsorption of the vapors produced by battery solvents or their degassing products, as well as water, to investigate the impact of humidity. PF5 and C4H10O2 showed the most exothermic molecular interactions, which are consistent with our gas response investigations. Our results indicate that humidity does not impact the performance of the sensors, which is crucial for the early detection of thermal runaway under harsh conditions in Li-ion batteries. We show that our semiconducting metal-oxide sensors can detect the vapors produced by battery solvents and degassing products with high accuracy and can serve as high-performance battery safety sensors to prevent explosions in malfunctioning Li-ion batteries. Despite the fact that the sensors work independently of the type of battery, the work presented here is of particular interest for the monitoring of solid-state batteries, since DOL is a solvent typically used in this type of batteries.

Oxygen diffusion in the orthorhombic FeNbO4 material: a computational study.

ABO4-type materials have shown significant potential for applications as luminescence and photocatalytic materials, and the orthorhombic FeNbO4 (o-FeNbO4) material has also shown excellent promise in catalytic electrodes, unlike other common ABO4 materials. However, little computational work has been carried out on the o-FeNbO4 structure, potentially because it is disordered and thus not straightforward to simulate. In this work, we first confirmed the accuracy of the force field parameters obtained from previous studies through optimizations carried out using the GULP code. Next, we found that one ordered configuration of the stoichiometric o-FeNbO4 structure dominates when analysing the probabilities of cation disorder in three supercells (2 × 2 × 1, 2 × 1 × 2, and 1 × 2 × 2). We then studied the bulk properties of this selected o-FeNbO4 through DFT calculations, including the lattice parameters, the mechanical properties and the electronic structures, where no remarkable differences were observed compared to the monoclinic FeNbO4 structure. Finally, because oxygen mobility is key to the successful application of o-FeNbO4 as an electrode material, we have simulated the diffusion pathways of oxygen through both the stoichiometric and non-stoichiometric structures, where the results show that the existence of oxygen vacancies enhances diffusion and the distribution of the Fe and Nb inside the lattice affects the energy barriers and could therefore impact the oxygen diffusion.

Catalytic formation of oxalic acid on the partially oxidised greigite Fe3S4(001) surface.

Greigite (Fe3S4), with its ferredoxin-like 4Fe-4S redox centres, is a naturally occurring mineral capable of acting as a catalyst in the conversion of carbon dioxide (CO2) into low molecular-weight organic acids (LMWOAs), which are of paramount significance in several soil and plant processes as well as in the chemical industry. In this paper, we report the reaction between CO2 and water (H2O) to form oxalic acid (H2C2O4) on the partially oxidised greigite Fe3S4(001) surface by means of spin-polarised density functional theory calculations with on-site Coulomb corrections and long-range dispersion interactions (DFT+U-D2). We have calculated the bulk phase of Fe3S4 and the two reconstructed Tasker type 3 terminations of its (001) surface, whose properties are in good agreement with available experimental data. We have obtained the relevant phase diagram, showing that the Fe3S4(001) surface becomes 62.5% partially oxidised, by replacing S by O atoms, in the presence of water at the typical conditions of calcination [Mitchell et al. Faraday Discuss. 2021, 230, 30-51]. The adsorption and co-adsorption of the reactants on the partially oxidised Fe3S4(001) surface are exothermic processes. We have considered three mechanistic pathways to explain the formation of H2C2O4, showing that the coupling of the C-C bond and second protonation are the elementary steps with the largest energy penalty. Our calculations suggest that the partially oxidised Fe3S4(001) surface is a mineral phase that can catalyse the formation of H2C2O4 under favourable conditions, which has important implications for natural ecosystems and is a process that can be harnessed for the industrial manufacture of this organic acid.

Al2O3/ZnO Heterostructure-Based Sensors for Volatile Organic Compounds in Safety Applications.

Monitoring volatile organic compounds (VOCs) in harsh environments, especially for safety applications, is a growing field that requires specialized sensor structures. In this work, we demonstrate the sensing properties toward the most common VOCs of columnar Al2O3/ZnO heterolayer-based sensors. We have also developed an approach to tune the sensor selectivity by changing the thickness of the exposed amorphous Al2O3 layer from 5 to 18 nm. Columnar ZnO films are prepared by a chemical solution method, where the exposed surface is decorated with an Al2O3 nanolayer via thermal atomic layer deposition at 75 °C. We have investigated the structure and morphology as well as the vibrational, chemical, electronic, and sensor properties of the Al2O3/ZnO heterostructures. Transmission electron microscopy (TEM) studies show that the upper layers consist of amorphous Al2O3 films. The heterostructures showed selectivity to 2-propanol vapors only within the range of 12-15 nm thicknesses of Al2O3, with the highest response value of ∼2000% reported for a thickness of 15 nm at the optimal working temperature of 350 °C. Density functional theory (DFT) calculations of the Al2O3/ZnO(1010) interface and its interaction with 2-propanol (2-C3H7OH), n-butanol (n-C4H9OH), ethanol (C2H5OH), acetone (CH3COCH3), hydrogen (H2), and ammonia (NH3) show that the molecular affinity for the Al2O3/ZnO(1010) interface decreases from 2-propanol (2-C3H7OH) ≈ n-butanol (n-C4H9OH) > ethanol (C2H5OH) > acetone (CH3COCH3) > hydrogen (H2), which is consistent with our gas response experiments for the VOCs. Charge transfers between the surface and the adsorbates, and local densities of states of the interacting atoms, support the calculated strength of the molecular preferences. Our findings are highly important for the development of 2-propanol sensors and to our understanding of the effect of the heterojunction and the thickness of the top nanolayer on the gas response, which thus far have not been reported in the literature.

Density Functional Theory Study of Ethylene Carbonate Adsorption on the (0001) Surface of Aluminum Oxide α-Al2O3.

Surface coating is one of the techniques used to improve the electrochemical performance and enhance the resistance against decomposition of cathode materials in lithium-ion batteries. Despite several experimental studies addressing the surface coating of secondary Li-ion batteries using α-Al2O3, the reactivity of the material toward the electrolyte components is not yet fully understood. Here, we have employed calculations based on the density functional theory to investigate the adsorption of the organic solvent ethylene carbonate (EC) on the major α-Al2O3(0001) surface. During adsorption of a single EC molecule, it was found that it prefers to bind parallel to the surface through its carboxyl oxygen. As the surface coverage (θ) was increased up to a monolayer, we observed larger adsorption energies per EC molecule (E ads/N EC) for parallel interactions and a reduction for perpendicular interactions. We also noted that increasing the surface coverage with both parallel and perpendicularly interacting EC molecules led to a decrease of the surface free energies and hence increased stability of the α-Al2O3(0001) surface. Despite the larger E ads/N EC observed when the molecule was placed parallel to the surface, minimal charge transfer was calculated for single EC interactions and at higher surface coverages. The simulated scanning tunneling microscopy images are also presented for a clean corundum α-Al2O3 surface and after adsorption with different coverages of parallel and perpendicularly placed EC molecules.

TiO2/Cu2O/CuO Multi-Nanolayers as Sensors for H2 and Volatile Organic Compounds: An Experimental and Theoretical Investigation.

TiO2/Cu2O/CuO multi-nanolayers highly sensitive toward volatile organic compounds (VOCs) and H2 have been grown in various thicknesses by a cost-effective and reproducible combined spray-sputtering-annealing approach. The ultrathin TiO2 films were deposited by spray pyrolysis on top of sputtered-annealed Cu2O/CuO nanolayers to enhance their gas sensing performance and improve their protection against corrosion at high operating temperatures. The prepared heterostructures were investigated using scanning electron microscopy (SEM), X-ray diffraction (XRD), and ultraviolet visible (UV-vis) and micro-Raman spectroscopy. The gas sensing properties were measured at several operating temperatures, where the nanolayered sensors with oxide thicknesses between 20 and 30 nm (Cu2O/CuO nanolayers) exhibited a high response and an excellent selectivity to ethanol vapor after thermal annealing the samples at 420 °C. The results obtained at an operating temperature of 350 °C demonstrate that the CuO/Cu2O nanolayers with thicknesses between 20 and 30 nm are sensitive mainly to ethanol vapor, with a response of ∼150. The response changes from ethanol vapors to hydrogen gas as the thickness of the CuO/Cu2O nanolayers changes from 50 to 20 nm. Density functional theory-based calculations were carried out for the geometries of the CuO(1̅11)/Cu2O(111) and TiO2(111)/CuO(1̅11)/Cu2O(111) heterostructures and their sensing mechanism toward alcohols of different chain lengths and molecular hydrogen. The reconstructed hexagonal Cu2O(111) surface and the reconstructed monoclinic CuO(1̅11) and TiO2(111) facets, all of which terminate in an O layer, lead to the lowest surface energies for each isolated material. We studied the formation of the binary and ternary heteroepitaxial interfaces for the surface planes with the best-matching lattices. Despite the impact of the Cu2O(111) substrate in lowering the atomic charges of the CuO(1̅11) adlayer in the binary sensor, we found that it is the different surface structures of the CuO(1̅11)/Cu2O(111) and TiO2(111)/CuO(1̅11)/Cu2O(111) devices that are fundamental in driving the change in the sensitivity response observed experimentally. The experimental data, supported by the computational results, are important in understanding the use of the multi-nanolayered films tested in this work as reliable, accurate, and selective sensor structures for the tracking of gases at low concentrations.

CO2 reduction to acetic acid on the greigite Fe3S4{111} surface.

Acetic acid (CH3-COOH) is an important commodity chemical widely used in a myriad of industrial processes, whose production still largely depends on homogeneous catalysts based on expensive rare metals. Here, we report a computational study on the formation of CH3-COOH from carbon dioxide (CO2) as an alternative chemical feedstock on the {111} surface of the low-cost greigite Fe3S4 catalyst. We have used density functional theory calculations with a Hubbard Hamiltonian approach and long-range dispersion corrections (DFT+U-D2) to simulate the various stages of the direct combination of C1 species of different composition to produce glyoxylic acid (CHO-COOH) as a key intermediate in the formation of CH3-COOH. Three reaction mechanisms are considered: (i) the main pathway where the direct formation of the C-C bond takes place spontaneously, followed by a step-wise reduction of CHO-CHOO to CH3-COOH; and the competitive pathways for the non-promoted and H-promoted elimination of hydroxy groups (OH) and water (H2O), respectively from (ii) the carboxyl; and (iii) the carbonyl end of the glyoxylate intermediates. The thermodynamic and kinetic profiles show that the energies for the intermediates on the main pathway are very similar for the two catalytic sites considered, although the activation energies are somewhat larger for the exposed tetrahedral iron (FeA) ion. In most cases, the intermediates for the deoxygenation of the carboxylic acid are less stable than the intermediates on the main pathway, which suggests that the molecule prefers to lose the carbonylic oxygen. The suitable surface properties of the Fe3S4{111} surface show that this material could be a promising sustainable catalyst in future technologies for the conversion of CO2 into organic acid molecules of commercial interest.

The role of surface oxidation and Fe-Ni synergy in Fe-Ni-S catalysts for CO2 hydrogenation.

Increasing carbon dioxide (CO2) emissions, resulting in climate change, have driven the motivation to achieve the effective and sustainable conversion of CO2 into useful chemicals and fuels. Taking inspiration from biological processes, synthetic iron-nickel-sulfides have been proposed as suitable catalysts for the hydrogenation of CO2. In order to experimentally validate this hypothesis, here we report violarite (Fe,Ni)3S4 as a cheap and economically viable catalyst for the hydrogenation of CO2 into formate under mild, alkaline conditions at 125 °C and 20 bar (CO2 : H2 = 1 : 1). Calcination of violarite at 200 °C resulted in excellent catalytic activity, far superior to that of Fe-only and Ni-only sulfides. We further report first principles simulations of the CO2 conversion on the partially oxidised (001) and (111) surfaces of stoichiometric violarite (FeNi2S4) and polydymite (Ni3S4) to rationalise the experimentally observed trends. We have obtained the thermodynamic and kinetic profiles for the reaction of carbon dioxide (CO2) and water (H2O) on the catalyst surfaces via substitution and dissociation mechanisms. We report that the partially oxidised (111) surface of FeNi2S4 is the best catalyst in the series and that the dissociation mechanism is the most favourable. Our study reveals that the partial oxidation of the FeNi2S4 surface, as well as the synergy of the Fe and Ni ions, are important in the catalytic activity of the material for the effective hydrogenation of CO2 to formate.

Atomistic Molecular Dynamics Simulations of Propofol and Fentanyl in Phosphatidylcholine Lipid Bilayers.

Atomistic molecular dynamics (MD) and steered MD simulations in combination with umbrella sampling methodology were utilized to study the general anesthetic propofol and the opioid analgesic fentanyl and their interaction with lipid bilayers, which is not yet fully understood. These molecules were inserted into two different fully hydrated phospholipid bilayers, namely, dioleoylphosphatidylcholine (DOPC) and dipalmitoylphosphatidylcholine (DPPC), to investigate the effects that these drugs have on the bilayer. We determined the role of the lipid chain length and saturation on the behavior of the two drugs. Pure, fully hydrated DOPC and DPPC bilayers were also simulated, and the results were in excellent agreement with the experimental values. Various structural and mechanical properties of each system, such as the area per lipid, area compressibility modulus, order parameter, lateral lipid diffusion, hydrogen bonds, and radial distribution functions, have been calculated to assess how the drug molecules affect the different bilayers. From the calculated results, we show that fentanyl and propofol generally follow similar trends in each bilayer but adopt different favorable positions close to the headgroup/chain interface at the carbonyl groups. Propofol was shown to selectively form hydrogen bonds at the carbonyl carbon in each bilayer, whereas fentanyl interacts with water molecules at the headgroup interface. From the calculated free-energy profiles, we determined that both molecules show a preference for the low-density, low-order acyl chain region of the bilayers and both significantly preferred the DOPC bilayer with propofol and fentanyl having energy minima at -6.66 and -43.07 kcal mol-1, respectively. This study suggests that different chain lengths and levels of saturation directly affect the properties of these two important molecules, which are seen to work together to control anesthesia in surgical applications.

Ethylene carbonate adsorption on the major surfaces of lithium manganese oxide Li1-xMn2O4 spinel (0.000 < x < 0.375): a DFT+U-D3 study.

Understanding the surface reactivity of the commercial cathode material LiMn2O4 towards the electrolyte is important to improve the cycling performance of secondary lithium-ion batteries and to prevent manganese dissolution. In this work, we have employed spin-polarized density functional theory calculations with on-site Coulomb interactions and long-range dispersion corrections [DFT+U-D3-(BJ)] to investigate the adsorption of the electrolyte component ethylene carbonate (EC) onto the (001), (011) and (111) surfaces of the fully lithiated and partially delithiated Li1-xMn2O4 spinel (0.000 < x < 0.375). The surface interactions were investigated by evaluating the adsorption energies of the EC molecule and the surface free energies. Furthermore, we analyzed the impact of EC adsorption on the Wulff crystal morphologies, the molecular vibrational frequencies and the adsorbate/surface charge transfers. The adsorption energies indicate that the EC molecule strongly adsorbs on the (111) facet, which is attributed to a bidentate binding configuration. We found that EC adsorption enhances the stability of the (111) facet, as shown by the Wulff crystal morphologies. Although a negligible charge transfer was calculated between the spinel surfaces and the EC molecule, a large charge rearrangement takes place within the surfactant upon adsorption. The wavenumbers of the C[double bond, length as m-dash]O stretching mode for the interacting EC molecule are red-shifted with respect to the isolated adsorbate, suggesting that this bond becomes weaker. The surface free energies show that both the fully lithiated and partially delithiated forms of the LiMn2O4 surfaces are stabilized by the EC molecule.

Tuning ZnO Sensors Reactivity toward Volatile Organic Compounds via Ag Doping and Nanoparticle Functionalization.

Nanomaterials for highly selective and sensitive sensors toward specific gas molecules of volatile organic compounds (VOCs) are most important in developing new-generation of detector devices, for example, for biomarkers of diseases as well as for continuous air quality monitoring. Here, we present an innovative preparation approach for engineering sensors, which allow for full control of the dopant concentrations and the nanoparticles functionalization of columnar material surfaces. The main outcome of this powerful design concept lies in fine-tuning the reactivity of the sensor surfaces toward the VOCs of interest. First, nanocolumnar and well-distributed Ag-doped zinc oxide (ZnO:Ag) thin films are synthesized from chemical solution, and, at a second stage, noble nanoparticles of the required size are deposited using a gas aggregation source, ensuring that no percolating paths are formed between them. Typical samples that were investigated are Ag-doped and Ag nanoparticle-functionalized ZnO:Ag nanocolumnar films. The highest responses to VOCs, in particular to (CH3)2CHOH, were obtained at a low operating temperature (250 °C) for the samples synergistically enhanced with dopants and nanoparticles simultaneously. In addition, the response times, particularly the recovery times, are greatly reduced for the fully modified nanocolumnar thin films for a wide range of operating temperatures. The adsorption of propanol, acetone, methane, and hydrogen at various surface sites of the Ag-doped Ag8/ZnO(0001) surface has been examined with the density functional theory (DFT) calculations to understand the preference for organic compounds and to confirm experimental results. The response of the synergistically enhanced sensors to gas molecules containing certain functional groups is in excellent agreement with density functional theory calculations performed in this work too. This new fabrication strategy can underpin the next generation of advanced materials for gas sensing applications and prevent VOC levels that are hazardous to human health and can cause environmental damages.

Mixing thermodynamics and electronic structure of the Pt1-x Ni x (0 ≤ x ≤ 1) bimetallic alloy.

The development of affordable bifunctional platinum alloys as electrode materials for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) remains one of the biggest challenges for the transition towards renewable energy sources. Yet, there is very little information on the optimal ratio between platinum and the transition metal used in the alloy and its impact on the electronic properties. Here, we have employed spin-polarised density functional simulations with long-range dispersion corrections [DFT-D3-(BJ)], to investigate the thermodynamics of mixing, as well as the electronic and magnetic properties of the Pt1-x Ni x solid solution. The Ni incorporation is an exothermic process and the alloy composition Pt0.5Ni0.5 is the most thermodynamically stable. The Pt0.5Ni0.5 solid solution is highly ordered as it is composed mainly of two symmetrically inequivalent configurations of homogeneously distributed atoms. We have obtained the atomic projections of the electronic density of states and band structure, showing that the Pt0.5Ni0.5 alloy has metallic character. The suitable electronic properties of the thermodynamically stable Pt0.5Ni0.5 solid solution shows promise as a sustainable catalyst for future regenerative fuel cells.

Thermal Properties and Segregation Behavior of Pt Nanowires Modified with Au, Ag, and Pd Atoms: A Classical Molecular Dynamics Study.

Platinum nanowires (NWs) have been reported to be catalytically active toward the oxygen reduction reaction (ORR). The edge modification of Pt NWs with metals M (M = Au, Ag, or Pd) may have a positive impact on the overall ORR activity by facilitating diffusion of adsorbed oxygen, Oads, and hydroxyl groups, OHads, between the {001} and {111} terraces. In the present study, we have employed classical molecular dynamics simulations to investigate the segregation behavior of Au, Ag, and Pd decorating the edges of Pt NWs. We observe that, under vacuum conditions, Pd prefers to diffuse toward the core rather than stay on the NW surface. Ag and Au atoms are mobile at temperatures as low as 900 K; they remain on the surface but do not appear to be preferentially more stable at edge sites. To effect segregation of Au and Ag atoms toward the edge, we propose annealing in the presence of different reactive gas environments. Overall, our study suggests potential experimental steps required for the synthesis of Pt nanowires and nanoparticles with improved Oads and OHads interfacet diffusion rates and consequently an improved ORR activity.

Interaction of H2O with the Platinum Pt (001), (011), and (111) Surfaces: A Density Functional Theory Study with Long-Range Dispersion Corrections.

Platinum is a noble metal that is widely used for the electrocatalytic production of hydrogen, but the surface reactivity of platinum toward water is not yet fully understood, even though the effect of water adsorption on the surface free energy of Pt is important in the interpretation of the morphology and catalytic properties of this metal. In this study, we have carried out density functional theory calculations with long-range dispersion corrections [DFT-D3-(BJ)] to investigate the interaction of H2O with the Pt (001), (011), and (111) surfaces. During the adsorption of a single H2O molecule on various Pt surfaces, it was found that the lowest adsorption energy (E ads) was obtained for the dissociative adsorption of H2O on the (001) surface, followed by the (011) and (111) surfaces. When the surface coverage was increased up to a monolayer, we noted an increase in E ads/H2O with increasing coverage for the (001) surface, while for the (011) and (111) surfaces, E ads/H2O decreased. Considering experimental conditions, we observed that the highest coverage was obtained on the (011) surface, followed by the (111) and (001) surfaces. However, with an increase in temperature, the surface coverage decreased on all the surfaces. Total desorption occurred at temperatures higher than 400 K for the (011) and (111) surfaces, but above 850 K for the (001) surface. From the morphology analysis of the Pt nanoparticle, we noted that, when the temperature increased, only the electrocatalytically active (111) surface remained.

CO2 interaction with violarite (FeNi2S4) surfaces: a dispersion-corrected DFT study.

The unbridled emissions of gases derived from the use of fossil fuels have led to an excessive concentration of carbon dioxide (CO2) in the atmosphere with concomitant problems to the environment. It is therefore imperative that new cost-effective catalysts are developed to mitigate the resulting harmful effects through the activation and conversion of CO2 molecules. In this paper, we have used calculations based on the density functional theory (DFT), including two semi-empirical approaches for the long-range dispersion interactions (-D2 and -D3), to explore the interaction of CO2 with the surfaces of spinel-structured violarite (FeNi2S4). This ternary sulfide contains iron ions in the highest possible oxidation state, while the nickel atoms are in the mixed 2+/3+ valence state. We found that CO2 interaction with violarite is only moderate due to the repulsion between the oxygen lone pairs and the electronic clouds of the sulfur surface atoms. This suggests that the CO2 activation is not dictated by the presence of nickel, as compared to the pure iron-isomorph greigite (Fe3S4). These results differ from findings in (Ni,Fe) ferredoxin enzymes, where the Ni/Fe ratio influences the redox potential, which suggests that the periodic crystal structure of violarite may hinder its redox capability.

Insight into the Nature of Iron Sulfide Surfaces During the Electrochemical Hydrogen Evolution and CO2 Reduction Reactions.

Greigite and other iron sulfides are potential, cheap, earth-abundant electrocatalysts for the hydrogen evolution reaction (HER), yet little is known about the underlying surface chemistry. Structural and chemical changes to a greigite (Fe3S4)-modified electrode were determined at -0.6 V versus standard hydrogen electrode (SHE) at pH 7, under conditions of the HER. In situ X-ray absorption spectroscopy was employed at the Fe K-edge to show that iron-sulfur linkages were replaced by iron-oxygen units under these conditions. The resulting material was determined as 60% greigite and 40% iron hydroxide (goethite) with a proposed core-shell structure. A large increase in pH at the electrode surface (to pH 12) is caused by the generation of OH- as a product of the HER. Under these conditions, iron sulfide materials are thermodynamically unstable with respect to the hydroxide. In situ infrared spectroscopy of the solution near the electrode interface confirmed changes in the phosphate ion speciation consistent with a change in pH from 7 to 12 when -0.6 V versus SHE is applied. Saturation of the solution with CO2 resulted in the inhibition of the hydroxide formation, potentially due to surface adsorption of HCO3-. This study shows that the true nature of the greigite electrode under conditions of the HER is a core-shell greigite-hydroxide material and emphasizes the importance of in situ investigation of the catalyst under operation to develop true and accurate mechanistic models.

Reactivity of CO2 on the surfaces of magnetite (Fe3O4), greigite (Fe3S4) and mackinawite (FeS).

The growing environmental, industrial and commercial interests in understanding the processes of carbon dioxide (CO2) capture and conversion have led us to simulate, by means of density functional theory calculations, the application of different iron oxide and sulfide minerals to capture, activate and catalytically dissociate this molecule. We have chosen the {001} and {111} surfaces of the spinel-structured magnetite (Fe3O4) and its isostructural sulfide counterpart greigite (Fe3S4), which are both materials with the Fe cations in the 2+/3+ mixed valence state, as well as mackinawite (tetragonal FeS), in which all iron ions are in the ferrous oxidation state. This selection of iron-bearing compounds provides us with understanding of the effect of the composition, stoichiometry, structure and oxidation state on the catalytic activation of CO2 The largest adsorption energies are released for the interaction with the Fe3O4 surfaces, which also corresponds to the biggest conformational changes of the CO2 molecule. Our results suggest that the Fe3S4 surfaces are unable to activate the CO2 molecule, while a major charge transfer takes place on FeS{111}, effectively activating the CO2 molecule. The thermodynamic and kinetic profiles for the catalytic dissociation of CO2 into CO and O show that this process is feasible only on the FeS{111} surface. The findings reported here show that these minerals show promise for future CO2 capture and conversion technologies, ensuring a sustainable future for society.This article is part of a discussion meeting issue 'Providing sustainable catalytic solutions for a rapidly changing world'.