Behavior Of Pd Research Articles

A C3‐Symmetric Structurally Twisted Molecular Architecture: Mechano‐/Fluorochromic Behavior and Selective Multiphase Detection of Pd(II)

AbstractTriaminoguanidinium (TG)‐based C3‐symmetric‐like molecular architectures with diverse donors and acceptors are well established as organic molecular materials for promising stimuli‐responsive and metal sensing‐based applications. However, the mechanofluorochromic (MFC) response was unremarkable upon applying external mechanical stress. Even though some show MFC features, there was no optical shift under ambient light. In this paper, we developed a novel C3‐symmetric molecule, TAC3, containing the TG core linked with conformationally twisted thiophene‐linked anthracenyl terminals. Three conformationally deformed hands in TAC3 respond against external mechanical stimuli with a redshifted absorption and emission, easily detectable through the naked eye. Although MFC features were reported before for such C3‐symmetric molecules, the change in absorbance was not identified. In addition, TAC3 could selectively detect Pd2+ through extreme emission quenching (green to black). The mechanochromism and sensing outcomes are elucidated by the experimental and theoretical support. Compared to the previous reports, the notable 2 : 3 (metal: ligand) binding due to geometric restriction creating a specific pocket size for Pd+2 is unusual for this system. The onsite application on Pd2+ detection and measurable MFC features are demonstrated to validate the potential of this C3‐symmetric molecule in advanced optoelectronic applications such as security writing and Pd2+ ion detection.

Efficient Electrocatalytic Hydrodechlorination and Detoxification of Chlorophenols by Palladium-Palladium Oxide Heterostructure.

Electrocatalytic hydrodechlorination is a promising approach for simultaneous pollutant purification and valorization. However, the lack of electrocatalysts with high catalytic activity and selectivity limits its application. Here, we propose a palladium-palladium oxide (Pd-PdO) heterostructure for efficient electrocatalytic hydrodechlorination of recalcitrant chlorophenols and selective formation of phenol with superior Pd-mass activity (1.35 min-1 mgPd-1), which is 4.4 times of commercial Pd/C and about 10-100 times of reported Pd-based catalysts. The Pd-PdO heterostructure is stable in real water matrices and achieves selective phenol recovery (>99%) from the chlorophenol mixture and efficient detoxification along chlorophenol removal. Experimental results and computational modeling reveal that the adsorption/desorption behaviors of zerovalent Pd and PdO sites in the Pd-PdO heterostructure are optimized and a synergy is realized to promote atomic hydrogen (H*) generation, transfer, and utilization: H* is efficiently generated at zerovalent Pd sites, transferred to PdO sites, and eventually consumed in the dechlorination reaction at PdO sites. This work provides a promising strategy to realize the synergy of Pd with different valence states in the metal-metal oxide heterostructure for simultaneous decontamination, detoxification, and resource recovery from halogenated organic pollutants.

Alloying effects on the reactivity of Pd are ensemble dominated

In this paper the geometric (“ensemble”) and electronic (“ligand”) effects of alloying on surface reactivity and catalysis are considered. The effect of alloying on the behaviour of Pd, both in single crystal form, and as a nanoparticulate catalyst is discussed. The first case concerns Pd alloyed with Cu, and here the reactivity with formic acid and ethanol is modified by the presence of Cu. However, both Cu and Pd maintain their elemental integrity for the reactions, and it is shown that the main alloying effect is one of dilution of Pd atoms, rather than by global electronic factors such as d-band shifting and filling. Similarly, when Pd is alloyed with Au, then the adsorption characteristics (sticking probability and uptake) for CO, O2, ethene and acetaldehyde are dominated by changes in the surface arrangement of the two atoms. Au mainly acts as an adsorption blocker, but to different degrees depending upon the nature of the adsorbing molecule and its demand for particular ensemble sizes. Finally, nanoparticulate Pd is considered, and the effect of alloying on high pressure methanol synthesis from CO2 and H2 is outlined. Pd on its own is not very selective, instead it mainly produces CO and methane. However, by supporting on oxides such as ZnO, Ga2O3 and In2O3 and by reducing in hydrogen, the Pd forms alloys, which then results in high selectivity to methanol. Again, this is ascribed to the dilution of the Pd ensembles at the surface, which are the cause of methane production.

Ethanol Oxidation Reaction on Electrodeposited Pd and Sb‒Pd Catalysts in Alkaline Solution Containing Na or Li Cations

Abstract This work reports the galvanostatical electrodeposition of Pd and Sb‒Pd catalysts on rotating glassy carbon (GC) electrode using surfactant-free electrolytes and the prepared catalysts were tested is the electro-oxidation reactions in alkaline solutions. Characterization of Pd and Sb‒Pd catalysts was performed with scanning electron microscope (SEM), energy-dispersive X-ray spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS) technique. Cyclic voltammetry (CV) and chronoamperometry were applied in order to study the electrocatalytic behavior of Pd and Sb‒Pd catalysts in the ethanol oxidation reaction (EOR) in alkaline solution containing Na+ or Li+ cations from the point of the impact of the selected alkali metal cations on the electrocatalytic activity. The peak current of EOR at Pd and Sb‒Pd catalysts in the solution with Li+ cations is 2.5 times higher compared to the values obtained in the solution with Na+ cations. EOR starts at rather negative potentials in LiOH solution regarding NaOH for approximately 0.03 V indicating the active role of OHad and the impact of the nature of alkali metal cations which consequently arises from the formation of OHad ‒ cation clusters. The role of Sb in bimetallic catalyst was established by adjusting the extent and persistence of OHad surface coverage.

Mixing behaviour and sources of Ag, Pd, and other trace elements in the Estuary and Gulf of St. Lawrence under winter conditions

The marine chemistry of platinum group elements is poorly documented despite robust evidence of their widespread emissions and deposition around the globe. Here, we report the concentrations and discuss the geochemical behaviours of Ag, Pd and other trace and ultra-trace elements in the Estuary and Gulf of St. Lawrence (EGSL). We highlight the contrasting mixing behaviours of these elements, i.e., conservative (Cd, Re) vs. non-conservative (Ag, Pd), in samples collected during the winter and under ice-covered conditions. We ascribe the contrasting geochemical behaviour of these elements to their differential affinity for reactive surfaces carried into the estuary from the frozen watersheds. We also report an increase of the concentrations of Ag (up to 40 pmol L−1), Pd (up to 10 pmol L−1) and Pt (up to 0.4 pmol L−1) in the bottom and oxygen-depleted waters of the Gulf of St. Lawrence (GSL). A strong correlation between dissolved Pt concentrations and the stable carbon isotopic composition of the dissolved inorganic carbon (δ13C-DIC) suggests that the increased mobility of Pt may result from the aerobic mineralization of organic carbon or the oxidation of Pt-bearing organic complexes. Molar Pt/Pd ratios in the three water masses that compose the water column in the EGSL highlight a potential influence of anthropogenic sources near urban centers. The signature of continental end-members will be required to confirm the impacts of road traffic on the estuarine geochemistry of these elements.

Crystal-Phase- and B-Content-Dependent Electrochemical Behavior of Pd─B Nanocrystals toward Oxygen Reduction Reaction.

The manipulation of crystal phases in metal-nonmetal interstitial alloy nanostructures has attracted considerable attention due to the formation of unique electronic structures and surface atomic arrangements, resulting in unprecedented catalytic performances. However, achieving simultaneous control over crystal phase and nonmetal elements in metal-nonmetal interstitial alloy nanostructures has remained a formidable challenge. Here, a novel synthesis approach is presented for Pd─B interstitial alloy nanocrystals (NCs) that allows investigation of the crystal-phase- and B-content-dependent catalytic performance. Through comparison of the oxygen reduction reaction (ORR) properties of Pd─BX interstitial alloy NCs with different crystal phases and B contents, achieved by precise control of reaction temperature and time, the influences of crystal phase and B contents in the Pd─BX interstitial alloy NCs on ORR are precisely investigated. The hexagonal closed packed (hcp) PdB0.5 NCs exhibit superior catalytic activity, with mass activities reaching 2.58 A mg-1, surpassing Pd/C by 10.3 times, attributed to synergistic effects by the hcp crystal phase and relatively high B contents. This study not only provides a novel approach to fabricate interstitial alloy nanostructures with unconventional crystal phases and finely controlled nonmetal elements but also elucidates the importance of crystal phase and nonmetal element content in optimizing electrocatalytic efficiency.

CO2 hydrogenation to methanol on intermetallic PdGa and PdIn catalysts and the effect of Zn co-deposition

The behaviour of Pd deposited on Ga2O3 and In2O3 by CVI is compared for the hydrogenation of CO2 to methanol. Ga2O3 alone is inactive, but In2O3 has good conversion, and selectivity as high as 89 % to CH3OH. The addition of Pd to the catalysts had relatively little effect for In2O3, but in contrast, the addition of Pd to Ga2O3, has a very big effect, inducing high activity and selectivity to methanol. Both oxides form Pd intermetallics - Pd2In3 and Pd2Ga. However, for the In catalysts there is also a thick (∼3 nm) overlayer of the oxide, while for the Ga catalyst there was no such overlayer. Hence this is why addition of Pd to the Indium catalysts has relatively little effect on performance compared with Ga. Furthermore, the effect of Pd and Zn co-deposition on Ga₂O₃ and In₂O₃ was investigated, as well as the effect of the support morphology. Upon co-deposition of Pd and Zn, and after reduction, the Pd2In3 catalyst remains phase stable, whereas the Pd2Ga alloy is replaced by PdZn, and is improved in methanol yield.

A pair of conjoined trinuclear sub-frameworks in a pentanuclear double-cavity discrete coordination cage.

Combination of Pd(ii) with selected bis-monodentate ligands produces the familiar multinuclear Pd m L2m type self-assembled "single-cavity discrete coordination cages" (SCDCC). If the ligand provides parallel coordination vectors, then it forms a binuclear Pd2L4 type cage, whereas utilization of ligands having appropriately divergent coordination vectors results in specific higher nuclear complexes. In contrast, preparation of emergent "multi-cavity discrete coordination cages" (MCDCC) using Pd(ii) and designer ligands is quite captivating where the neighboring cavities of the framework are conjoined with each other through a common metal center. A pair of conjoined binuclear Pd2L4 type sub-frameworks are present in a trinuclear Pd3L4 type double-cavity cage prepared from Pd(ii) and a tris-monodentate ligand having parallel coordination vectors. The present work envisioned a design to make double-cavity coordination cages having a pair of conjoined trinuclear Pd3L6 type sub-frameworks. To fulfill the objective we combined Pd(ii) with a mixture of designer bis-monodentate ligand (L) and tris-monodentate ligand (L') in a 5 : 4 : 4 ratio in one pot to afford the targeted pentanuclear type cage. The choice of bis-monodentate ligand L is based on the divergent nature of the coordination vectors suitable to produce a Pd3L6 type SCDCC. The tris-monodentate ligand L' having two arms is designed in such a manner that each of the arms reasonably resembles L. Study of the complexation behavior of Pd(ii) with L' provided additional guiding factors essential for the successful making of type MCDCC by integrative self-sorting. A few other MCDCC including lower symmetry versions were also prepared in the course of the work.

Synthesis and comparative study of (NHCF)PdCl2Py and (NHCF)Ni(Cp)Cl complexes: investigation of the electronic properties of NHC ligands and complex characteristics.

The electron-donating and electron-accepting properties of N-heterocyclic carbene (NHC) ligands play a pivotal role in governing their interactions with transition metals, thereby influencing the selectivity and reactivity in catalytic processes. Herein, we report the synthesis of Pd/NHCF and Ni/NHCF complexes, wherein the electronic parameters of the NHC ligands were systematically varied. By performing a series of controlled structure modifications, we elucidated the influence of the σ-donor and π-acceptor properties of NHC ligands on interactions with the transition metals Pd and Ni and, consequently, the catalytic behavior of Pd and Ni complexes. The present study deepens our understanding of NHC-metal interactions and provides novel information for the rational design of efficient catalysts for organic synthesis.

Understanding the Adsorption Behavior and Mechanism of Pt(IV) and Pd(II) on Super Amino-Modified Monodispersed PGMA Microspheres

Understanding the Adsorption Behavior and Mechanism of Pt(IV) and Pd(II) on Super Amino-Modified Monodispersed PGMA Microspheres

Close accord on partial discharge diagnosis during voltage harmonics in electric motors fed by variable frequency drives

AbstractPartial discharge (PD) diagnostics test is a reliable solution for estimating insulation health conditions in power system components. During laboratory PD diagnostics, the effect of harmonic components in the voltage waveform generated by variable frequency drives (VFD) fed electric motors (EMs) is often overlooked. As VFD‐fed EMs operate at low speeds, the harmonic concentration in the voltage increases. It has been found that PD activity in VFD‐fed EM is significantly affected by the addition of harmonic components in the voltage, thus making it necessary to consider their impact when performing true PD diagnostics. This paper investigates the influence of voltage harmonic distortion produced in VFD‐fed EM on PD severity and the subsequent insulation degradation. Eight VFD‐fed EM are used to study the PD behaviour under different levels of harmonic pollution. The PD characteristics, such as inception voltage, pulse repetition rate, accumulated apparent charge, average discharge current, discharge power, and quadratic rate, are determined. Using probability distribution functions, PD activity and severity at various voltage harmonic levels are estimated. The proposed technique can be used to plan the maintenance activities that ensure the reliability for industrial applications dealing with the voltage harmonic distortion.

Effect of Supporting Pd Nanoparticles on WOx Nanorods on Their Stability and Catalytic Activity Towards the Electrochemical Oxidation of Concentrated Formic Acid

Direct formic acid fuel cells (DFAFC) are considered one of the most promising fuel cells to penetrate the market due to their desired and unique properties. Formic acid (FA) could be easily produced from different sources (especially biomass) and is non-toxic. The FA-based fuel cell has a high open circuit potential in comparison to methanol and Ethanol1, high energy conversion efficiency, and fast kinetics. However, the major drawback that affects using DFAFCs is the catalysts' stability and reaction intermediates' poisoning effect, especially at high concentrations of FA.FA has a dual pathway mechanism: either the simple and desired pathway of direct oxidation to CO2 2 or the unfavorable indirect oxidation to poisonous CO-like species that strongly adsorb on the catalyst surface, deactivating it,3 before it is hardly oxidized in a second step to give CO2. Therefore, the catalyst should be designed to direct the reaction towards the direct pathway and facilitate the poisoning species removal. The most active catalyst for FA oxidation in acidic media is palladium4 but it is highly susceptible to CO poisoning, especially as the FA concentration increases due to the high contribution of the indirect pathway. In addition, palladium nanoparticles supported on carbon material are known to suffer from dissolution in the acidic media making the electrode unstable for long-term application.5 In this presentation, the synthesis of nonstoichiometric WOx nanorods using hydrothermal methods will be reported. The Pd nanoparticles are synthesized and loaded on the WOx nanorods using ethanol as both a solvent and a reducing agent to produce a surfactant-free Pd surface. The synthesized materials are evaluated using XRD, TEM, FT-IR, EDS, and XPS. The effect of WOx nanorods as catalyst support on Pd nanoparticles activity and stability towards the oxidation of different concentrations (1-4 M) of FA in acidic media are evaluated using cyclic voltammetry (CV) and chronopotentiometry (CP), and compared with that of carbon-supported Pd catalyst. The Pd behavior in both cases will be correlated to its chemical and physical properties and thoroughly discussed.

Population Target-Mediated Pharmacokinetic/Pharmacodynamic Modeling to Evaluate SPI-62 Exposure and Hepatic 11β-Hydroxysteroid Dehydrogenase Type 1 (HSD-1) Inhibition in Healthy Adults.

SPI-62 is a small-molecule 11β-hydroxysteroid dehydrogenase type 1 (HSD-1) inhibitor exhibiting complicated nonlinear pharmacokinetics (PK) in human. Previously, we developed a target-mediated drug disposition (TMDD) model to characterize the substantial nonlinear PK of SPI-62. The aim of the current analysis was to perform population PK/PD analysis to further link SPI-62 exposure (i.e., PK) with its response (i.e., inhibition of hepatic HSD-1 activity) to gain a quantitative understanding of the SPI-62 dose-exposure-response relationship. PK and PD data from the first-in-human (FIH) clinical trials, including single ascending dose (SAD) and multiple ascending dose (MAD) studies, were used for model development. During the model development process, the final model selection was based on biological and physiological plausibility, goodness-of-fit plots, stability of parameter estimates, and objective function value. The nonlinear-mixed effect modeling (NONMEM) software was used for both the implementation of the PK/PD model and model simulation. SPI-62 plasma levels and hepatic HSD-1 inhibition over time following various dose regimens were simulated. The final model was a two-compartment TMDD model component for SPI-62 and an inhibitory Imax model component for hepatic HSD-1 activity. The TMDD-hepatic PD model that we established adequately characterized all remarkable PK and PD behaviors of SPI-62, such as extremely low plasma exposures following the first low doses, nonlinear PK turned into linear PK after repeated low doses, and substantial and long-lasting hepatic HSD-1 inhibition following low doses. SPI-62 was estimated to bind to the target with a second-order association rate constant (Kon) of 8.43 nM-1h-1 and first-order dissociation rate constant (Koff) value of 0.229 h-1, indicating that SPI-62 binds rapidly to, and dissociates slowly from, its pharmacological target. The estimated target capacity (Rtot) of 5460 nmol corresponds to approximately 2.2 mg of SPI-62, which comports well with the dose range in which PK nonlinearity is prominent. Model simulation results reveal that a 6 mg once-daily regimen can lead to long-lasting and substantial hepatic HSD-1 inhibition. A population TMDD-PD model that explains SPI-62 nonlinear PK and hepatic HSD-1 inhibition following different dose regimens in healthy adults was successfully established. Our simulation results provide a solid foundation for model-informed development of SPI-62.

Adsorption of Pd(II) ions by electrospun fibers with effective adsorption sites constructed by N, O atoms with a particular spatial configuration: Mechanism and practical applications

The separation and recovery of palladium from electronic waste (e-waste) are of great significance as they can alleviate environmental pollution and avoid resource loss. Herein, a novel nanofiber modified by 8-hydroxyquinoline (8-HQ-Nanofiber) with adsorption sites co-constructed by N and O atoms of hard bases was fabricated, which has good affinity properties for the Pd(II) ions belonging to soft acid in the leachate of e-waste. The adsorption mechanism of 8-HQ-Nanofiber for Pd(II) ions was revealed from the perspective of molecular level relied on a series of characterizations, such as FT-IR, ss-NMR, Zeta potential, XPS, BET, SEM and DFT. The adsorption of Pd(II) ions on 8-HQ-Nanofiber reached equilibrium within 30 min and the maximum uptake capacity was 281 mg/g at 318.15 K. The adsorption behavior of Pd(II) ions by 8-HQ-Nanofiber was described by the pseudo-second-order and Langmuir isotherm models. The 8-HQ-Nanofiber exhibited relatively good adsorption performance after 15 times of column adsorption. Finally, based on hard and soft acids and bases (HSAB) theory, a strategy to regulate the Lewis alkalinity of adsorption sites by specific spatial structures is proposed, which provides a new direction for the design of adsorption sites.

Clozapine-loaded nanocapsules improve antipsychotic activity in rats: building a sequential PopPK/PD model to discriminate nanocarriers in the preformulation step.

We investigated the impact of nanoformulations on the dose-exposure-response relationship of clozapine (CZP), a low-solubility antipsychotic with serious adverse effects, using a popPK/PD approach. We evaluated the pharmacokinetics and PK/PD profiles of three coated polymeric CZP-loaded nanocapsules functionalized with polysorbate 80 (NCP80), polyethylene glycol (NCPEG), and chitosan (NCCS). Data on in vitro CZP release by dialysis bag, plasma pharmacokinetic profiles in male Wistar rats (n = 7/group, 5 mg kg-1, i.v.), and percentage of head movements in a stereotyped model (n = 7/group, 5 mg kg-1, i.p.) were integrated using a sequential model building approach (MonolixSuiteTM-2020R1-Simulation Plus). A base popPK model developed with CZP solution data collected after the i.v. administration of CZP was expanded to describe the changes in drug distribution caused by nanoencapsulation. Two additional compartments were inserted into the NCP80 and NCPEG models, and a third compartment was included in the NCCS model. The nanoencapsulation showed a decrease in the central volume of distribution for NCCS (V1NCpop = 0.21 mL), while for FCZP, NCP80, and NCPEG, it was ~1 mL. The peripheral distribution volume was higher for the nanoencapsulated groups (19.1 and 129.45 mL for NCCS and NCP80, respectively) than for FCZP. The popPK/PD model showed a formulation-dependent plasma IC50, with 20-, 50-, and 80-fold reductions compared to the CZP solution (NCP80, NCPEG, and NCCS, respectively). Our model discriminates the coatings and describes the peculiar PK and PD behavior of nanoencapsulated CZP, especially NCCS, making it an exciting tool for evaluating the preclinical performance of nanoparticles.

Complexation and Separation of Palladium with Tridentate 2,6-Bis-triazolyl-pyridine Ligands: Synthesis, Solvent Extraction, Spectroscopy, Crystallography, and DFT Calculations.

Selective extraction of palladium from high-level liquid waste (HLLW) is desirable for the sustainable development of nuclear energy and resource recovery. In this work, three tridentate 2,6-bis-triazolyl-pyridine ligands (L-I, L-II, and L-III) bearing different alkyl side chains were synthesized and systematically studied for the complexation and extraction of palladium. Altering the alkyl side chains of the ligands led to pronounced differences in extraction performance. Among the three ligands, L-II decorated with two n-octyl groups exhibited the highest Pd(II) extraction efficiency at acidity levels of 1-5 M HNO3 and outstanding selectivity over 13 coexisting competing metal ions. Results from UV-vis titration experiments and theoretical calculations suggested that the differentiated extraction abilities of the ligands could be because of their different hydrophilicity rather than electron-donating effects. Slope analyses and electrospray ionization-high resolution mass spectrometry (ESI-HRMS) experiments revealed the formation of both L/Pd 1:1 and 2:1 species during the extraction process. These stoichiometries were further confirmed by job plots and NMR titration experiments. The ligands were found to aggregate slightly, especially at higher concentrations, which could result from multiple intermolecular hydrogen bonds as illustrated by X-ray crystallography. The configurations of PdL and PdL2 were further elucidated by analysis of single crystal structure and density-functional theory (DFT) calculations, respectively, where the first coordination sphere of Pd(II) was surrounded by four nitrogen or oxygen atoms in a quadrangular manner. This study provides an alternative method to separate palladium from HLLW and brings a new understanding of the coordination and complexation behaviors of Pd(II) with tridentate nitrogen ligands.

Effects of Oxygen Plasma Treatment on Fermi‐Level Pinning and Tunneling at the Metal–Semiconductor Interface of WSe2 FETs

AbstractRecently, 2D materials have been intensively investigated for their novel nanoelectronic applications; among these materials, tungsten diselenide (WSe2) is attracting substantial research interest due to its high mobility, sizable bandgap, and ambipolar characteristics. However, Fermi‐level pinning (FLP) at the metal–semiconductor contact is a critical issue preventing further integration of WSe2 to complementary metal–oxide–semiconductor (CMOS) technology. In this study, a facile doping method of oxygen (O2) plasma treatment and an aging effect to overcome the FLP of WSe2 field‐effect transistors (FETs) are utilized. After aging, a reduction is observed in FLP on oxidized WSe2 FETs, along with a decrease in pinning factor (S) for holes from −0.06 to −0.36. Further, the field‐effect mobility of high‐ (Pd) and low‐ (In) work‐function contacted WSe2 devices indicates the presence of more improvement in high‐work‐function metal‐contacted p‐type WSe2 FETs, which further strengthens the Fermi level de‐pinning behavior attributed to the O2 plasma and aging processes. The existence of different tunneling behaviors of Pd and In devices also confirms the effect of O2 plasma doping into WSe2 FETs. Ultimately, this work demonstrates a simple and efficient method for achieving the de‐pinning of Fermi‐levels and modulating FLP of 2D FETs.

DFT study on the adsorption of CO, NO2, SO2 and NH3 by Te vacancy and metal atom doped MoTe2 monolayers

Based on the first-principles calculation, the adsorption structure and electronic characteristics of CO, NO 2 , SO 2 and NH 3 adsorbed on pure, defective and metal atom doped MoTe 2 monolayer were systematically studied. The original MoTe 2 monolayer and MoTe 2 monolayer containing Te defects can be used as room temperature gas sensors to detect NO 2 gas and SO 2 gas, and the adsorption effect can steadily increase in the simulated working environment. The adsorption behaviors of Ag, Pd and Rh atoms with different doping methods were studied. The calculation results show that the conductivity and chemical activity between metal atoms and gas is improved after doping, resulting in tremendous adsorption energy and charge transfer. Due to the changes in the energy band structure, the density of states, work function and recovery time after adsorption, different doped systems show the potential of high-performance gas sensors at room temperature and high temperature. The research results are significant to the gas sensing mechanism of the modified MoTe 2 monolayer and helpful in exploring the modified MoTe 2 monolayer as a sensing material and gas scavenger. • MoTe 2 containing defects can improve gas adsorption capacity, especially for SO 2 molecules. • Two methods of metal atom doping can improve the chemical activity of gas and substrate. • The adsorption structures under different systems were explored as gas sensors and scavengers.

Understanding the Reactivity of Supported Late Transition Metals on a Bare Anatase (101) Surface: A Periodic Conceptual DFT Investigation.

The rapidly growing interest for new heterogeneous catalytic systems providing high atomic efficiency along with high stability and reactivity triggered an impressive progress in the field of single-atom catalysis. Nevertheless, unravelling the factors governing the interaction strength between the support and the adsorbed metal atoms remains a major challenge. Based on periodic density functional theory (DFT) calculations, this paper provides insight into the adsorption of single late transition metals on a defect-free anatase surface. The obtained adsorption energies fluctuate, with the exception of Pd, between -3.11 and -3.80 eV and are indicative of a strong interaction. Depending on the considered transition metal, we could attribute the strength of this interaction with the support to i) an electron transfer towards anatase (Ru, Rh, Ni), ii) s-d orbital hybridisation effects (Pt), or iii) a synergistic effect between both factors (Fe, Co, Os, Ir). The driving forces behind the adsorption were also found to be strongly related to Klechkowsky's rule for orbital filling. In contrast, the deviating behaviour of Pd is most likely associated with the lower dissociation enthalpy of the Pd-O bond. Additionally, the reactivity of these systems was evaluated using the Fermi weighted density of states approach. The resulting softness values can be clearly related to the electron configuration of the catalytic systems as well as with the net charge on the transition metal. Finally, these indices were used to construct a model that predicts the adsorption strength of CO on these anatase-supported d-metal atoms. The values obtained from this regression model show, within a 95 % probability interval, a correlation of 84 % with the explicitly calculated CO adsorption energies.

Plastic deformation behavior of Pd-based binary alloys: A first-principles study

The generalized stacking fault energy is a critical parameter for plastic deformation and phase transition behavior of alloys. Here, the generalized stacking fault energies of palladium-based binary alloys (Pd 1− x M x , M = Mo, W, Re, Ru, Os, Rh, Ir, Pt; x = 0, 0.1, 0.2, 0.3, 0.4, 0.5) in face-centered cubic (fcc) phase are systematically investigated by combining the coherent potential approximation with the exact muffin-tin orbital method within the framework of density functional theory. Analysis of the plastic behavior of Pd 1− x M x reveals that Mo, W, Re, Ru, and Os alloying elements can promote twinning, which in turn can be used to strengthen Pd alloys. When alloying reaches up to 30 at.% Mo, 40 at.% W, or 40 at.% Re, phase transition from fcc to hexagonal compact packing and stacking faults are the primary deformation of Pd 1− x M x . Contrarily, Rh, Ir, and Pt significantly suppress the twinning ability, and full slip becomes the dominant deformation mechanism. Such distinct deformation behavior of Pd-based alloys is attributed to their electron redistribution upon alloying, owing to the d - d hybridization between alloy elements and Pd atoms. This study gives valuable insight into the phase stability and provides useful guide for the design of high-strength alloys. • Alloying rich Mo, W, and Re into Pd promotes the phase transition from fcc to hcp. • Alloying elements Mo, W, Re, Ru, and Os can promote twinning mechanism of Pd 1−x M x . • Rh, Ir, and Pt alloying with Pd would facilitate full slip deformation. • Deformation of Pd 1−x M x is related to d-d hybridization between alloy atoms and Pd.