Incorporating Transition Metal Research Articles

Scalable bottom-up synthesis of Co-Ni-doped graphene.

Introducing heteroatoms into graphene is a powerful strategy to modulate its catalytic, electronic, and magnetic properties. At variance with the cases of nitrogen (N)- and boron (B)-doped graphene, a scalable method for incorporating transition metal atoms in the carbon (C) mesh is currently lacking, limiting the applicative interest of model system studies. This work presents a during-growth synthesis enabling the incorporation of cobalt (Co) alongside nickel (Ni) atoms in graphene on a Ni(111) substrate. Single atoms are covalently stabilized within graphene double vacancies, with a Co load ranging from 0.07 to 0.22% relative to C atoms, controllable by synthesis parameters. Structural characterization involves variable-temperature scanning tunneling microscopy and ab initio calculations. The Co- and Ni-codoped layer is transferred onto a transmission electron microscopy grid, confirming stability through scanning transmission electron microscopy and electron energy loss spectroscopy. This method holds promise for applications in spintronics, gas sensing, electrochemistry and catalysis, and potential extension to graphene incorporation of similar metals.

Hydrothermal synthesis of rGO and MnCoS composite for enhanced supercapacitor application

Nanostructured materials incorporating transition metal sulfides have demonstrated considerable potential across various applications, particularly in the realms of energy production and storage. Sulfide-based material preparation is a challenging and costly procedure that requires a high temperature and reducing atmosphere. This work reports that manganese cobalt sulfide (MCS) and reduced graphene oxide composite manganese cobalt sulfide (rMCS) were successfully prepared through a hydrothermal method. Various characterization techniques were employed to analyze the prepared materials, including X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, Brunauer-Emmett-Teller analysis, and X-ray photoelectron spectroscopy. In a three-electrode system, MCS and rMCS electrodes exhibit an excellent specific capacitance of 1695 and 1925 F g−1 at 1 A g−1 current density respectively. MCS delivers the capacitance retention of 99% and rMCS exhibits the capacitance retention of 100% capacitance retention over 5000 consecutive cycles. The constructed asymmetric supercapacitor electrode (rMCS//rGO) exhibits the energy and power density of 64 Wh kg−1 at 799 W kg−1, respectively with outstanding cyclic stability of 97.4% even after 10,000 cycles. The exceptional electrochemical properties of MCS with rGO composite electrode indicate that they would make an outstanding electrode material for cutting-edge energy storage devices.

Effect of incorporated transition metals on the adsorption mechanisms of radioactive cesium in Prussian blue analogs

Extensive efforts were made to remove radioactive cesium (137Cs) from the environment, with Prussian blue analogs (PBAs) emerging as highly selective and efficient materials for 137Cs removal. However, limited studies systematically compared Cs+ adsorption across different transition metals in PBA. This study investigates the influence of the choice of transition metal ion (Co, Cu, Fe, Mn, Ni, Zn) on Cs+ adsorption mechanisms and efficiency. PBAs were synthesized and characterized based on their specific surface area, ion exchange capacity, lattice parameter, and defect sites (as indicated by water molecule content). Cs+ adsorption mechanisms varied significantly with transition metals. In CoFe and FeFe PBAs, ion exchange with K+ dominated, while CuFe and MnFe PBAs, with more defect sites primarily used ion exchange between H+ and Cs+. NiFe and ZnFe exhibited enhanced Cs+ adsorption under light irradiation, likely due to their light-absorbing properties facilitating a reduction reaction. The Langmuir adsorption isotherm was applied to model the adsorption behavior, confirming that each performance of PBA depends on the transition metal used. These findings suggest that PBAs with various transition metals can efficiently remove 137Cs under diverse environmental conditions by using distinct adsorption mechanisms.

Constructing electrochemically stable single crystal Ni-rich cathode material via modification with high valence metal oxides

Single crystal Ni-rich cathode materials (SCNCM) are a good supplement in the market of nickel-based materials due to their safety and excellent electrochemical performance. However, the challenges of cation mixing, phase change during charge/discharge, and low thermal stability remain unresolved in single crystal particles. To address these issues, SCNCM are rationally modified by incorporating transition metal (TM) oxides, and the influence of metal ions with different valence states on the electrochemical properties of SCNCM is methodically explored through experimental results and theoretical calculations. Enhanced structural stability is demonstrated in SCNCM after the modifications, and the degree of improvement in the matrix materials varies depending on the valence state of doped TM ions. The highest structural stability is found in WO3-modified SCNCM, due to the smaller effective ion radii, higher electro-negativity, stronger W–O bond, and efficient suppression of oxygen vacancy generation. As a result, WO3-modified SCNCM have outstanding cycle performance, with a capacity retention rate of 90.2% after 200 cycles. This study provides an insight into the design of advanced SCNCM with enhanced reversibility and cyclability.

Screening Transition-Metal-Incorporated β-AgVO3 for Augmented Oxygen Reduction Activity.

Exploring cost-effective alternatives to Pt-based catalysts for the oxygen reduction reaction (ORR) in fuel cells is crucial for their large-scale deployment in green energy applications. Silver vanadate (AgVO3) is a well-studied material for photocatalytic applications. Here, we investigate the electrocatalytic ORR activity of the thermodynamically stable β phase of AgVO3 through computational modeling based on DFT. It is found that β-AgVO3 exhibits weak catalytic activity for the ORR, with vanadium being the preferable active site. Incorporating single atoms of transition metals at surface-level vacancies in β-AgVO3 significantly modifies the ORR activity. We study the scaling of free energy changes for the ORR intermediates *OOH, *OH, and *O for various transition metals incorporated, which leads to an optimal overpotential for the system. The optimal overpotential thus obtained is remarkably lower than that of pristine β-AgVO3. For the transition metal atoms we consider here, Co-incorporated β-AgVO3 exhibits the best ORR catalytic activity due to its optimal binding of ORR species to the vanadium site. It is also observed that some of the transition metals considered like Re, Rh, Os, or Mn show weak activity, either due to strong or weak binding. Analysis of the electronic structure of the adsorbate-catalyst interface shows a strong correlation between optimal activity and evolution of midgap states in β-AgVO3, due to transition metal incorporation. Our study concludes that the ORR activity of a stable mixed transition metal oxide like β-AgVO3 can be enhanced with a minimal loading of transition metals, which could help in developing a novel series of ORR catalysts.

Sc/Y/Ti functionalized N-substituted defective C24 as promising materials for hydrogen storage

Incorporating transition metal atoms and creating porphorin-like N4 cavity are effective strategies for improving the hydrogen storage capability of carbon materials. In this view, we designed and addressed the hydrogen uptake properties of TM4C8N8 (TM = Sc, Y, Ti) cages originating from C24 to overcome TM clustering. The stabilities of three clusters were confirmed by molecular dynamic simulation. Sc4C8N8/Y4C8N8/Ti4C8N8 can bind up to 20/20/36H2 molecules with a higher gravimetric density of 9.35/6.67/15.27 wt%, compared to the goal of 5.5 wt% proposed by the US-DOE. The interaction between H2 molecules and the hosts can be identified as van der Waals attractions. The average binding energies of Sc4C8N8(H2)20/Y4C8N8(H2)20/Ti4C8N8(H2)36 at M06(D3) and PBE(D3) functional are 0.159/0.173/0.128 eV/H2 and 0.139/0.141/0.102 eV/H2, respectively, meeting the desirable range of reversible hydrogen storage. Furthermore, an investigation was conducted on the impact of pressure and temperature on the hydrogen storage capabilities of TM4C8N8 (TM = Sc, Y, Ti). The desorption temperature exhibits a positive correlation with increasing pressure. The realization of hydrogen release at near mild conditions and the reversibility of hydrogen adsorption/desorption cycles were demonstrated using the van't Hoff equation and ADMP-MD simulations, respectively. Compared with the monomer, the hydrogen storage capacities of (TM4C8N8)2 (TM = Sc, Y, Ti) dimers are slightly reduced.

1D Lead Bromide Hybrids Directed by Complex Cations: Syntheses, Structures, Optical and Photocatalytic Properties.

This study presents the synthesis, structural characterization, and evaluation of the photocatalytic performance of two novel one-dimensional (1D) lead(II) bromide hybrids, [Co(2,2'-bpy)3][Pb2Br6CH3OH] (1) and [Fe(2,2'-bpy)3][Pb2Br6] (2), synthesized via solvothermal reactions. These compounds incorporate transition metal complex cations as structural directors, contributing to the unique photophysical and photocatalytic properties of the resulting materials. Single-crystal X-ray diffraction analysis reveals that both compounds crystallize in monoclinic space groups with distinct 1D lead bromide chain configurations influenced by the nature of the complex cations. Optical property assessments show band gaps of 3.04 eV and 2.02 eV for compounds 1 and 2, respectively, indicating their potential for visible light absorption. Photocurrent measurements indicate a significantly higher electron-hole separation efficiency in compound 2, correlated with its narrower band gap. Additionally, photocatalytic evaluations demonstrate that while both compounds degrade organic dyes effectively, compound 2 also exhibits notable hydrogen evolution activity under visible light, a property not observed in 1. These findings highlight the role of metal complex cations in tuning the electronic and structural properties of lead(II) bromide hybrids, enhancing their applicability in photocatalytic and optoelectronic devices.

Superhydrophilic and Underwater Superaerophobic Dual-Function Peony-Shaped Selenide Micro-nano Array Self-Supported Electrodes for High-Efficiency Overall Water Splitting Driven by Renewable Energy.

With the intensification of global environmental pollution and resource scarcity, hydrogen has garnered significant attention as an ideal alternative to fossil fuels due to its high energy density and nonpolluting nature. Consequently, the urgent development of electrocatalytic water-splitting electrodes for hydrogen production is imperative. In this study, a superwetting selenide catalytic electrode with a peony-flower-shaped micronano array (MoS2/Co0.8Fe0.2Se2/NixSey/nickel foam (NF)) was synthesized on NF via a two-step hydrothermal method. The optimal catalytic activity of cobalt-iron selenide was achieved by adjusting the Co/Fe ratio. The intrinsic catalytic activity of the electrodes was enhanced by incorporating transition metal selenides, which then served as a precursor for the subsequent loading of MoS2 nanoflowers on the surface to fully expose the active sites. Furthermore, the superwetting properties of the electrode accelerated electrolyte penetration and electron/mass transfer, while also facilitating bubble detachment from the electrode surface, thereby preventing "bubble shielding effect". This resulted in superior oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) performance, as well as overall water splitting capabilities. In a 1.0 M KOH solution, the electrode required only 166 and 195 mV overpotential to achieve a current density of 10 mA cm-2 for OER and HER, respectively. When functioning as a bifunctional catalytic electrode, only 1.60 V of voltage was necessary to drive the electrolyzer to reach a current density of 10 mA cm-2. Moreover, laboratory simulations of wind and solar energy-driven water splitting validated the feasibility of establishing a sustainable energy-to-hydrogen production chain. This work provides new insights into the preparation of low-overpotential, high-catalytic-activity superhydrophilic and underwater superaerophobic catalytic electrodes by rationally adjusting elemental ratios and exploring changes in electrode surface wettability.

Transition metal embedded MoS2 as efficient trifunctional electrocatalyst: A computational study

In the advancement of electrochemical energy systems, multifunctional catalysts for the oxygen reduction reaction (ORR), hydrogen evolution reaction (HER), and oxygen evolution reaction (OER) are indispensable. Moreover, catalysts produced by incorporating transition metals into two-dimensional materials via substitutional modification have demonstrated remarkable efficacy. The present study examines the prospective uses of transition metal (TM= Nb, Co, In, and Re) dopants comprising 10% Niobium, Rhenium, Cobalt, and Indium in 2D MoS2. The density functional theory has been utilized to study the atomic level interaction. Based on the result, it can be observed that Nb-doped MoS2 has a ΔGH value of 0.06 eV, which signifies its remarkable HER capability when compared to pristine MoS2 and other doped versions. Our analysis for OER and ORR activities reveals that Co doped MoS2 exhibit superior performance compared to both the pristine and other doped versions of TM-MoS2, with an overpotential value ɳOER = 1.00 V and ɳORR = 0.77 V. A modification in electronic properties is examined by analysing the partial density of states during the HER and OER processes. The number of potential candidates suggested by the present findings will aid in the development of TM-doped MoS2-based electrocatalysts.

Incorporating Transition Metal Ions into Uranium Oxide Hydrates: The Role of Zn(II) and the Effect of the Addition of Cs(I) Ions.

The synthesis of two zinc-bearing uranium oxide hydrate (UOH) materials has been achieved, and their crystal structures, obtained via single-crystal X-ray diffraction using synchrotron radiation, and additional structural and spectroscopic properties are reported herein. Although both structures incorporate Zn2+ cations, the two differ significantly. The compound Zn2(OH)2(H2O)5[(UO2)10UO14(H2O)3] (UOHF-Zn), forming a framework-type structure in the P1̅ space group, was composed of β-U3O8 layers pillared by uranyl polyhedra, with the Zn2+ cations incorporated within the framework channels. In contrast, the compound Cs2Zn(H2O)4[(UO2)4O3(OH)4]2·3H2O (UOH-Zn) crystallized in the Cmc21 space group with a schoepite-like uranyl oxide hydroxide layered topology and both Zn2+ and Cs+ cations making up the interlayer species. The apparent driving force for the differences in the structures was the change from KOH to CsOH during synthesis, with the smaller K+ ions excluded in lieu of a higher proportion of Zn2+ (U/Zn ratio of 5.5:1) in UOHF-Zn, whereas in UOH-Zn, the larger Cs+ ions were preferentially incorporated at the expense of fewer Zn2+ cations (U/Cs/Zn ratio of 8:2:1). Highlighted in this work is the effect of the chemical species and, in particular, their ionic radius on UOH formation, further improving the understanding of UO2 alteration in the setting of deep geological repositories.

Research on the Construction of a Series of Transition Metal-Substituted Keggin-Type TMSPOMs@PCN-224 Composites through the Encapsulation Method and Their Electron Transfer Mechanism in CO2RR.

In order to take advantage of the distinct reversible multielectron transfer properties of polyoxometalates (POMs) and increase the electron density at the active sites during the electrochemical reduction of CO2 (CO2RR), a range of transition metal-doped polyoxometalates (TMSPOMs) was entrapped within the porphyrin-based framework of PCN-224 via an encapsulation method, known as TMSPOMs@PCN-224 (TMSPOMs = [XW11O39MII(H2O)]n-, [XW11O40VIV]n-, M = CoII, MnII; X = Si, n = 6; X = P, n = 5). The central elements (Si, P) and the incorporated transition metals (VIV, CoII, and MnII) both play a role in adjusting the electronic structure and electron transfer during the CO2RR process. Remarkably, the composite material with cobalt substitution displayed significantly improved performance. Through fine-tuning the POM loading, the electrocatalytic activity was optimized, leading to an impressive Faradaic efficiency for CO production (FECO) of 89.9% for SiW11Co@PCN-224, a significant improvement compared to the 12.1% FECO of PCN-224. Furthermore, the electrochemical stability of this catalyst was demonstrated over 20 h. Comparative analyses involving six composite materials indicated a relationship between the negative charge of the polyanions and their ability to facilitate effective electron transfer, ultimately enhancing the catalyst's performance. Meanwhile, these findings were supported by density functional theory (DFT) calculations.

Theoretical research on efficient electrocatalysis of CO2 reduction reaction by borophene loaded transition metals

Electrocatalytic conversion of CO2 into chemical or fuel is regarded as a viable approach to attain energy conversion, chemical energy storage and carbon neutrality. Borophene exhibits great potential as an electrocatalyst owing to its exceptional physical and chemical attributes. β12-borophene incorporated transition metal (TM) as single atom catalysts (SACs) have been devised for the electrocatalysis of the carbon dioxide reduction reaction (CO2RR). Through the exploration of the most favorable CO2RR pathway and the comparison of Gibbs free energy (ΔG) during the potential determination step (PDS), the catalyst exhibiting remarkable catalytic activity for CO2RR are chosen. Wherein, the overpotential of Nb-β12 and Ru-β12 produce CO is only 0.02 and 0.03 V. The overpotential of Ru-β12 and Rh-β12 in generation of HCOOH product is only 0.03 and 0.06 V. Additionally, the catalytic performance of Rh-β12 in CO2 reduction to CH3OH and CH4 showcases exceptional performance, with overpotential of 0.65 and 0.79 V. Unexpectedly, the overpotential of Cd-β12 and Mo-β12 are 0.01 and 0.09 V for hydrogen evolution reaction (HER). The research offers invaluable insight for systematic designs and screening of catalysts for the electrochemical CO2RR.

Hierarchical heterostructure Ni2P hollow carbon spheres derived from MOFs for efficient electromagnetic wave absorption

In this study, a hierarchical heterogeneous structure of Ni2P hollow carbon spheres (Ni2P-HCS) was synthesized through a two-step process involving carbonization and phosphorization of Ni-metal organic framework (Ni-MOF) precursors. During the construction of the Ni2P/C nanostructure, heterointerface recombination and secondary graphitization were observed, which contribute to the modulation of interface polarization. Structural analysis revealed that the Ni2P/C nanoparticles are uniformly dispersed, forming stable porous structured microspheres, thereby leveraging dielectric and magnetic losses. The combination of Ni2P with metal-organic frameworks (MOFs) can optimize impedance matching, enhance effective absorption bandwidth, and consequently improve electromagnetic wave absorption performance. The results show that Ni2P-HCS (Ni2P-HCS700) exhibited superior electromagnetic wave (EMW) absorption characteristics when the carbonization temperature is 700 ℃. It achieves a maximum reflection loss (RL) of −46.7 dB at a thickness of 2.9 mm and an effective absorption bandwidth (EAB) of 4.8 GHz at 1.71 mm thickness, almost covering the Ku-band (13.3 GHz−18 GHz). Radar cross-section (RCS) simulations utilizing CST indicated an optimal RCS reduction value of 41 dB m² at theta=0° for Ni2P-HCS700. This work introduces a universal approach to designing high-performance lightweight absorbers derived from MOFs, incorporating transition metal phosphides to form composites for impedance matching control.

Robust Room Temperature Thermoelectric Performance of Mg3(Sb, Bi)2‐Based Alloys via Multivalent Mn Doping

Abstractn‐type Mg3(Sb, Bi)2 has excellent room temperature thermoelectric performance, which is, however, severely restricted by the negatively charged Mg vacancies that significantly deteriorate the carrier mobility. Herein, by manipulating the threshold solubility and defect formation energy of Mn, multivalent Mn is selectively introduced that synergistically promotes the carrier conduction according to different Mg chemical potentials; In Mg‐rich areas, interstitial Mn dominates which effectively reduces the migration and accumulation of Mg vacancies, while in Mg poor areas, interstitial Mn switches to substitutional sites that directly compensate for the negative charge. All the Mn centers possess Jahn–Teller inactive positions, leading to an ultra‐stable room temperature thermoelectric performance with a leading ZT up to 0.97. This work reveals the critical effect of multivalent and multifunctional transition metal incorporation in Mg3(Sb, Bi)2‐based alloys toward high room‐temperature thermoelectric performance.

Steering lithium and potassium storage mechanism in covalent organic frameworks by incorporating transition metal single atoms

Organic electrodes mainly consisting of C, O, H, and N are promising candidates for advanced batteries. However, the sluggish ionic and electronic conductivity limit the full play of their high theoretical capacities. Here, we integrate the idea of metal-support interaction in single-atom catalysts with π-d hybridization into the design of organic electrode materials for the applications of lithium (LIBs) and potassium-ion batteries (PIBs). Several types of transition metal single atoms (e.g., Co, Ni, Fe) with π-d hybridization are incorporated into the semiconducting covalent organic framework (COF) composite. Single atoms favorably modify the energy band structure and improve the electronic conductivity of COF. More importantly, the electronic interaction between single atoms and COF adjusts the binding affinity and modifies ion traffic between Li/K ions and the active organic units of COFs as evidenced by extensive in situ and ex situ characterizations and theoretical calculations. The corresponding LIB achieves a high reversible capacity of 1,023.0 mA h g-1 after 100 cycles at 100 mA g-1 and 501.1 mA h g-1 after 500 cycles at 1,000 mA g-1. The corresponding PIB delivers a high reversible capacity of 449.0 mA h g-1 at 100 mA g-1 after 150 cycles and stably cycled over 500 cycles at 1,000 mA g-1. This work provides a promising route to engineering organic electrodes.

Magnetically engineering enhanced EMA property through high entropy transition metal ions within all-inorganic perovskite

Addressing challenges such as signal interference and crosstalk requires the development of new materials capable of electromagnetic absorption (EMA). In this study, we explored magnetically high-entropy engineering by incorporating transition metal ions into the B sites of all-inorganic CsPbBr3 perovskite. This approach yielded excellent EMA properties, including a minimum reflection loss of 75 dB at 10.2 GHz with a thickness of 2.5 mm and an effective bandwidth of 8.8 GHz. Fe, Co, Ni, and Mn ions were successfully introduced into the CsPbBr3 lattice using high-energy ball milling and the combustion method. Through rigorous characterization techniques such as Rietveld refinement of X-ray diffraction and Grazing-Incidence Wide-Angle Scattering patterns, we confirmed the presence of high-entropy phases. Additionally, we conducted comprehensive studies using Vibrating-sample magnetometer, L2,3 edge XANES, and Mossbauer spectra to investigate the magnetic polarization, spin states, and dipolar exchanges of the transition metal ions. The observed synergistic effects among the magnetic permeability, polarization, and magnetic loss of these ions underscored their role in enhancing the EMA performance of CsPbBr3.

Pre-implanting metal oxides to endow the N-doped carbon with boosted bifunctional catalytic activities towards oxygen reduction and oxygen evolution reactions

Nitrogen-doped carbon-based materials exhibit promising prospect as the catalysts to oxygen reduction reaction (ORR). Incorporating transition metal oxides with the catalysts can endow them with oxygen evolution reaction (OER) activity to construct bifunctional catalysts for rechargeable zinc-air batteries. In this work, a catalyst (named as 300NiFe-Mi-C) was prepared by a metal oxide-implanting strategy. The mixed metal salts of Ni and Fe were first heated to produce metal oxides, and then blended with 2-methylimidazole and carbon black, and subsequently pyrolyzed at a high temperature. In the pyrolysis, a part of metal oxides was reduced to metallic state to facilitate the doping of nitrogen atoms into carbon to form the ORR active sites while a part of metal oxides was retained to afford OER activity. Benefiting from the pre-implanting strategy of metal oxides, the resultant 300NiFe-Mi-C presents enhanced OER performance with 1.56 V of OER potential at 10 mA cm−2, outperforming the 1.68 V of the controlled sample NiFe-Mi-C (without pre-implanting) and 1.70 V of RuO2. The 0.83 V of ORR half-wave potential of 300NiFe-Mi-C is also comparable to the 0.82 V of NiFe-Mi-C and 0.86 V of Pt/C, revealing satisfactory bifunctional catalytic activities. The rechargeable zinc-air battery equipped with 300NiFe-Mi-C can stably operate at ∼1.25 V with 10 mA cm−2, being higher than ∼1.21 V of Pt/C+RuO2. The battery also presents outstanding durability and rechargeability, demonstrating the bifunctional activities of 300NiFe-Mi-C can be realized in practical applications.

Unlocking the potential of V/Ti-AAC: a promising eco-friendly catalyst for cyclohexene epoxidation

Abstract Bentonite is an abundant natural resource in the Maghnia region of Algeria that may have potential value in catalysis, but heretofore has been considered of low value for this purpose due to its low acidity and low catalytic activity. Low cost is one of the main criteria for choosing a suitable material for catalysis. Because bentonite is abundant and low-cost, its use as a starting material for the preparation of catalysts deserves reconsideration. The present study was undertaken, therefore, to optimize the performance of bentonite as a catalyst in one of the most promising reactions in organic synthesis, namely, cyclohexene epoxidation. The bentonite was subjected to adjustment of its structure by means of a number of laboratory treatments based on its large cation exchange capacity. These modifications aimed to achieve an environmentally friendly catalytic process by incorporating transition metals, specifically titanium and vanadium, into the modified bentonite structure through acid activation. Redox properties were enhanced and Lewis and Brønsted acidities were introduced. The vanadium oxide, supported on titania-pillared, acid-activated bentonite (5V/Ti-AAC), was characterized comprehensively using various techniques, including diffuse-reflectance UV-visible spectroscopy (DR UV-Vis), Fourier-transform infrared spectroscopy (FTIR) for surface acidity analysis, X-ray diffraction (XRD), nitrogen adsorption-desorption isotherms, and scanning electron microscopy (SEM) coupled with energy-dispersive X-ray elemental analysis (EDX). The catalytic activity was investigated in response to certain variables, such as catalyst mass, nature of the solvent, amount of oxidant, and reaction temperature. A kinetic study was conducted to understand the reaction behavior. The experimental results demonstrated intriguing catalytic activity, achieving a 42% conversion rate with ~68% selectivity toward the epoxide product when employing tert-butyl hydroperoxide (TBHP) as the oxidant and heptane as the solvent. This study highlights the potential of 5V/Ti-AAC as an environmentally friendly catalyst applied in the epoxidation of cyclohexene.

Transition metal incorporation: electrochemical, structure, and chemical composition effects on nickel oxyhydroxide oxygen-evolution electrocatalysts

Trace metal cations dissolved in alkaline electrolytes incorporate into nickel hydroxide/oxyhydroxide through in situ cation exchange, creating an interstratified structure near the surface of the material that impacts the electrochemical performance.

Conductance and assembly of quasi-1D coordination chain molecular junctions with triazole derivatives.

Incorporating transition metal atoms into metal-molecule-metal junctions presents opportunities for exploring the electronic properties of coordination complexes, organometallics and metal-organic materials on the single molecule level. Recent single molecule conductance studies have shown that in situ incorporation of electrode metal atoms into coordination chains formed in the junction can occur with deprotonated, negatively charged organic ligands, such as the imidazolate (Im-) anion. However, the mechanism and chemical principles, such as the role of the charge state of the ligand, for the construction of such coordination chains are still debated. Here, we probe the role of the ligand charge state and electronic structure in single-molecule conductance and formation of metal-molecule coordination chains. We perform break junction measurements with triazole isomers, which can bridge junctions both in their neutral and charged forms, and find that prior deprotonation of the ligands is not required for coordination complex assembly, but can affect the molecular conductance and junction formation probability. Our results indicate that coordination chains can form with neutral ligands, as long as the electron density in the frontier MOs is concentrated at the binding sites and along the direction of pulling, promoting ligand binding and incorporation of gold atoms into the junction during elongation. Our findings may provide insight into design principles for in situ assembled molecular wires with transition metal atoms and open the door to electronic and spintronic studies of such materials.