Bridging Oxygen Atoms Research Articles

Graphene Oxide-Enhanced Nucleation and Growth of Calcium-Silicate-Hydrate Gel at Nanoscale: A Molecular Dynamics Study.

Graphene oxide (GO) enhances the performance of cement-based materials by optimizing the microstructure of calcium-silicate-hydrate (C-S-H). However, the influence of GO on the nucleation and growth of C-S-H gel at nanoscale is unexplored. This study investigates this mechanism by molecular dynamics simulation at nano scale. Results show that GO can reduce the activation energy during the polymerization reaction of silicon oxide tetrahedra during the reaction process, and can increase the content of polymer Q3 and Q4. The influence of GO with epoxy (-O-), hydroxyl (-OH) and carboxyl (-COOH) groups on the radial distribution function (RDF), mean square displacement (MSD), and atomic spatial distribution of monomers are studied. Results show that GO-OH exhibits excellent performance, with the highest number of bridging oxygen atoms (about 0.6), the lowest Q0 monomer content (just 26.8%), the highest RDF (27.18), and the highest MSD (calcium and silicon content around 20,000 Å2). This paper elucidates the nucleation and growth mechanism of C-S-H influenced by GO to develop high performance cement.

Dinuclear Copper(II) Complex with Intramolecular O–H⋅⋅⋅O Hydrogen Bonding: Magneto‐Structural Correlation for Acylhydrazone‐Based Phenoxido Bridged Copper(II) Complexes

The μ‐phenoxido‐bridged dinuclear copper(II) complex, [Cu2(L1)2(dmso)(MeOH)] (1), has been synthesized using N′‐(4‐(diethylamino)‐2‐hydroxybenzylidene)‐1‐naphthohydrazide (H2L1) as ligand. The structural analysis of 1 reveals that the coordination geometry at the copper ions is best described as a square pyramidal with a Cu···Cu distance in the dinuclear complex of 303 pm which is supported by hydrogen bonding between the two apical oxygen donor ligands (O···O 277 pm). Magnetic studies indicate that 1 exhibits a strong antiferromagnetic interaction between the two copper(II) ions with a coupling constant of J = −450 cm−1. The magnetic exchange is transmitted through the central [Cu2(OR)2]2+ core, a fragment for which different magneto‐structural correlations have been reported depending on the substituent at the bridging oxygen atom. However, the properties of complex 1 cannot be explained by any of the established correlations. Nevertheless, complex 1, together with the series of compounds based on an acylhydrazone ligand framework reported so far, shows a magneto‐structural correlation as a function of the Cu−O−Cu bridging angle that significantly differs from all previously reported.

Structure and dynamic viscosity of CaO–SiO2 and CaO–SiO2–B2O3 model slag systems

Correlation dependencies between the dynamic viscosity of slag and its structural parameters were studied to determine an optimal basicity of silicon smelting slag under the addition of boron oxide to eliminate slagging of the bottom of ore-smelting furnaces. Experimental studies were conducted on CaO–SiO2 and CaO– SiO2–B2O3 model slags obtained at 1600°С. Raman spectroscopic analysis was carried out using a Horiba JobinYvon HR800UV analyzer (France). Theoretical calculations of slag viscosity were performed using Urbain and Mills models. During the experiments, the key structural parameters of slag systems varied within the following limits: the experimental Raman spectrum deconvolution function from 1.41 to 2.45 and optical basicity from 0.58 to 0.68. The obtained experimental and theoretical data were related by mathematical dependencies. It was found that the dynamic viscosity of slag can be promptly determined by Raman spectroscopy on the basis of mathematical models. The dependence obtained shows that slag viscosity decreases upon an increase in the number of bridging oxygen atoms in the silicate anion structure. Notably, this decrease in slag viscosity is observed up to the value of the experimental Raman spectrum deconvolution function of ~1.55-1.60 or slag optical basicity of 0.60–0.62. When B2O3 is added, the viscosity undergoes a further decrease. In practice, for CaO–SiO2 slag systems, the use of boroncontaining flux as a liquefying agent is reasonable at CaO/SiO2 = 0.61–0.63 while maintaining the content of B2O3 in the slag at a level of 1%. The two models (classical and modified) proposed by Urbain were established to be more suitable for theoretical calculation of viscosity in CaO–SiO2 and CaO–SiO2–B2O3 systems. Mills’ model is not suitable for these purposes, since the correlation coefficients in the corresponding mathematical model are not sufficiently large. Further research in this direction is required in order to establish appropriate dependencies of slag viscosity on its structural parameters at different temperatures.

Transformations to the aluminum coordination environment and network polymerization in amorphous aluminosilicates under pressure.

The structure of calcium aluminosilicate glasses (CaO)x(Al2O3)y(SiO2)1-x-y with the near tectosilicate compositions x ≃ 0.19 and 1 - x - y ≃ 0.61 or x ≃ 0.26 and 1 - x - y ≃ 0.49 was investigated by in situ high-pressure neutron diffraction and 27Al nuclear magnetic resonance (NMR) spectroscopy. The results show three distinct pressure regimes for the transformation of the aluminum coordination environment from tetrahedral to octahedral, which map onto the deformations observed in the production of permanently densified materials. The oxygen packing fraction serves as a marker for signaling a change to the coordination number of the network forming motifs. For a wide variety of permanently densified aluminosilicates, the aluminum speciation shares a common dependence on the reduced density ρ' = ρ/ρ0, where ρ is the density and ρ0 is its value for the uncompressed material. The observed increase in the Al-O coordination number with ρ' originates primarily from the formation of six-coordinated aluminum Al(VI) species, the fraction of which increases rapidly beyond a threshold ρthr'∼ 1.1. The findings are combined to produce a self-consistent model for pressure-induced structural change. Provided the glass network is depolymerized, one-coordinated non-bridging oxygen atoms are consumed to produce two-coordinated bridging oxygen atoms, thus increasing the network connectivity in accordance with the results from 17O NMR experiments. Otherwise, three-coordinated oxygen atoms or triclusters appear, and their fraction is quantified by reference to the mean coordination number of the silicon plus aluminum species. The impact of treating Al(VI) as a network modifier is discussed.

Robust Bi/MGO-COOH Composite for Electrochemical Sensing of Unsymmetrical Dimethylhydrazine Promoted by Lewis Acid-Base Interaction and Electric Field Forces

By integrating Lewis Acid-base and Internal Electro Field (IEF) into the design of a composite electrode material that does not rely on precious metals, this research aims to improve the detection of unsymmetrical dimethylhydrazine (UDMH), a hazardous environmental pollutant. This innovative approach addresses high costs and low sensitivity, enhancing detection in environmental monitoring and remediation. The hydrogen bond generated by Lewis Acid–Base and the IEF interactions produced by the bridging oxygen atoms on Bi surfaces interact synergistically to enhance the physical and chemical adsorption of UDMH, leading to its oxidation to CH3N=CH2. The method involves growing vertically aligned bismuth nanoflower electrodes (Bi NFs) on the carboxylated monolayer graphene oxide (MGO-COOH) surface, significantly enhancing UDMH detection sensitivity by 10.7 times within a range of 0.1 to 1 μg∙L−1, with a low detection limit of 0.525 μg∙L−1 and excellent recovery rates ranging from 94% to 108%. The electrodetection and electrooxidation mechanism of UDMH molecules by Bi NFs/MGO-COOH/GCE were further explored with density functional theory (DFT) and Fourier-transform infrared spectroscopy (FT-IR). This work demonstrates the cost-effective, highly sensitive detection of UDMH using Lewis Acid-Base and IEF surface interactions.

Enhanced Electrical Conductivity of Polyoxometalates by Bridging with Mixed‐Valent Multinuclear Platinum Complexes

AbstractPolyoxometalates (POMs) are nanosized molecular metal oxide anion clusters with tuneable structures and functionalities, and they exhibit a redox chemistry and catalytic activity in multielectron redox processes. These are typically poor electrical conductors (<10−10 Scm−1), which is attributed to negligible electronic interactions among anions in the solid state. Since the reduced electrons on the d0 metals in POMs are delocalized, electrical conductivity was improved when judicious pathways for the electrons were created by bridging the POMs. Utilized with the electronic interactions between bridging oxygen atoms with the highest occupied molecular orbital in the POMs and the metal dz2 orbitals in the multinuclear platinum complexes, and three mixed‐valent assemblies were synthesized and characterized. Simply mixing Keggin‐type or Dawson‐type POMs with tetranuclear or trinuclear platinum complexes in solution afforded three single crystals, and all three compounds were paramagnetic with mixed oxidation states and better conductivities at room temperature than the parent compounds.

Structural characterization of gallium fluoride phosphate glasses by advanced solid‐state NMR methods and correlation with photophysical properties

AbstractGallium fluoride phosphate glasses feature low refractive index, high energy radiation resistance, wide transmission range, and favorable emission characteristics of rare‐earth dopants. For the development of optimized glass compositions, a fundamental understanding of these properties in terms of glass structure is sought. We report nuclear magnetic resonance (NMR) structural studies of glasses in the system xGa(PO3)3–(40 − x)GaF3–20BaF2–20ZnF2–20SrF2 (x = 5, 10, 15, 20, and 25 mol%). 31P NMR results with 71Ga recoupling show that the network structure is dominated by P–O–Ga linkages, and no P–O–P linkages exist. 71Ga NMR results show that Ga is mainly six‐coordinated featuring a mixed fluoride/phosphate coordination. Quantitative estimates of this ligand distribution around gallium were obtained by 71Ga{31P} spin echo double resonance (REDOR) measurements. Photophysical properties suggest changes in the Eu(III) ligand distribution toward a fluoride‐dominated environment at low P/F ratio while the glass network is largely sustained by bridging oxygen atoms via P–O–Ga linkages.

Enhanced Electrical Conductivity of Polyoxometalates by Bridging with Mixed-Valent Multinuclear Platinum Complexes.

Polyoxometalates (POMs) are nanosized molecular metal oxide anion clusters with tuneable structures and functionalities, and they exhibit a redox chemistry and catalytic activity in multielectron redox processes. These are typically poor electrical conductors (<10-10 Scm-1), which is attributed to negligible electronic interactions among anions in the solid state. Since the reduced electrons on the d0 metals in POMs are delocalized, electrical conductivity was improved when judicious pathways for the electrons were created by bridging the POMs. Utilized with the electronic interactions between bridging oxygen atoms with the highest occupied molecular orbital in the POMs and the metal dz2 orbitals in the multinuclear platinum complexes, and three mixed-valent assemblies were synthesized and characterized. Simply mixing Keggin-type or Dawson-type POMs with tetranuclear or trinuclear platinum complexes in solution afforded three single crystals, and all three compounds were paramagnetic with mixed oxidation states and better conductivities at room temperature than the parent compounds.

Structures of Large Tin(IV) Oxo Clusters

AbstractThe article reviews and categorizes the structures of tin oxo clusters with nuclearities ≥6 and compares them with oxo clusters of the other group 4 and 14 metals. Basic construction principles of the cluster core are worked out by comparing the different cluster types and by identifying smaller building blocks. The comparison also shows how the different cluster types are influenced by the interplay between the ligands which stabilize the cluster core and the bridging oxygen atoms.

A (2-(Pyrrolidin-1-yl)ethan-1-olate)(1-oxo-3-phenyl-1,4-dihydronaphthalen-2-olate) μ-Oxo-Bridged Dicopper(II) Dimeric Complex

The reaction of 2-(1H-pyrrol-1-yl)ethanol with 3-hydroxyflavone in the presence of copper(II) bromide yielded a dimeric copper(II) complex, [μ-O-(κ2-O,O-flav)(κ2-N,O-2PEO)Cu]2 (1) (flav = 3-hydroxyflavonolate; 2PEO = 2-(1H-pyrrol-1-yl)ethanolate) with both the flav and 2PEO ligands bound to the copper(II) atom in a κ2-bonding mode. The dimer is held electrostatically by bridging oxygen atoms between two copper atoms. Complex 1 was characterized by single-crystal X-ray diffraction, infrared, and UV-Vis spectroscopy, elemental analysis, and melting point determination. The complex crystallizes in the monoclinic space group P21/n (14) with cell values of a = 11.85340(10) Å, b = 8.51480(10) Å, c = 23.8453(2) Å; β = 99.3920(10)°.

Exploring the effect of Er2O3 content on the structural, thermal, and physical characteristics of zinc silicate glasses

Glasses of chemical formula xEr2O3. (55-x) ZnO. 45SiO2 (x = 0, 0.5, 1, 3, 5, 7, 10, and 15 mol. %) were prepared using the melt-quenching route. The structure of the glasses was investigated by X-ray diffraction (XRD), Fourier transform infrared (FTIR), Raman, and NMR spectroscopy. XRD data confirmed that all zinc silicate glasses containing Er2O3 had an amorphous glassy structure. XRD showed the presence of two humps around 50° and 60° that are related to Er and Zn ions incorporated into the glass structure, and these humps' intensity changed with Er2O3 addition. The fraction of different silicate structural units is studied using FTIR and Raman spectroscopy, which is comparable to that obtained from the reported NMR values. FTIR, Raman, and NMR measurements confirmed the dual role of Er2O3 on the structure of zinc silicate glasses. Based on these results, Er2O3 content is below 5 mol. % entered as a glass modifier, creating more non-bridging oxygen atoms (NBO, increases Q1) while above 5 mol. % played a glass former, creating more bridging oxygen atoms (BO, increases Q2). Thermal heat treatment was applied for all glass samples according to DSC measurements. The thermal parameters have been discussed and correlated with the glass structure. The glass transition temperature (Tg) escalated from 377.3 at 5 mol. % to 391.04 °C at 15 mol. % Er2O3. The crystallization temperature (Tc) also increased from 548.27 °C to 598.37 °C, and the Vickers hardness (Hv) improved markedly from 646.4 kg/mm2 at 0 mol. % to 732.2 kg/mm2 at 15 mol. % Er2O3. XRD and FTIR results for glass samples after heat treatment for 24 h at 700 °C have been discussed regarding the crystallization of the glass matrix. These findings highlight the critical role of Er2O3 in modifying glass structure and properties, demonstrating its potential to enhance the glass matrix's durability and mechanical strength.

Structural Chemistry of Titanium (IV) Oxo Clusters, Part 2: Clusters without Carboxylate or Phosphonate Ligands.

Homometallic titanium oxo clusters (TOC) are one of the most important groups of metal oxo clusters. In a previous article, TOC structures with carboxylato and phosphonato ligands were reviewed and categorized. This work is now extended to clusters with other ligands. Comparison of the different cluster types shows how the interplay between condensation of the titanium polyhedra by means of bridging oxygen atoms and the coordination characteristics of the ligands influences the cluster structures and allows working out basic construction principles of the cluster core.

Molecular Insights into Sequence-Specific Protein Hydrolysis by a Soluble Zirconium-Oxo Cluster Catalyst.

The development of catalysts for controlled fragmentation of proteins is a critical undertaking in modern proteomics and biotechnology. {Zr6O8}-based metal-organic frameworks (MOFs) have emerged as promising candidates for catalysis of peptide bond hydrolysis due to their high reactivity, stability, and recyclability. However, emerging evidence suggests that protein hydrolysis mainly occurs on the MOF surface, thereby questioning the need for their highly porous 3D nature. In this work, we show that the discrete and water-soluble [Zr6O4(OH)4(CH3CO2)8(H2O)2Cl3]+ (Zr6) metal-oxo cluster (MOC), which is based on the same hexamer motif found in various {Zr6O8}-based MOFs, shows excellent activity toward selective hydrolysis of equine skeletal muscle myoglobin. Compared to related Zr-MOFs, Zr6 exhibits superior reactivity, with near-complete protein hydrolysis after 24 h of incubation at 60 °C, producing seven selective fragments with a molecular weight in the range of 3-15 kDa, which are of ideal size for middle-down proteomics. The high solubility and molecular nature of Zr6 allow detailed solution-based mechanistic/interaction studies, which revealed that cluster-induced protein unfolding is a key step that facilitates hydrolysis. A combination of multinuclear nuclear magnetic resonance spectroscopy and pair distribution function analysis provided insight into the speciation of Zr6 and the ligand exchange processes occurring on the surface of the cluster, which results in the dimerization of two Zr6 clusters via bridging oxygen atoms. Considering the relevance of discrete Zr-oxo clusters as building blocks of MOFs, the molecular-level understanding reported in this work contributes to the further development of novel catalysts based on Zr-MOFs.

Effect of B2O3 and Basic Oxides on Network Structure and Chemical Stability of Borosilicate Glass

Glass properties play crucial roles in ensuring the safety and reliability of electronic packaging. However, challenges, such as thermal expansion and resistance to acid corrosion, pose long-term service difficulties. This study investigated the impact of the microstructure on acid resistance by adjusting the glass composition. A glass material with excellent acid resistance was obtained by achieving a similar coefficient of thermal expansion to tantalum; it exhibited a weight loss rate of less than 0.03% when submerged in 38% sulfuric acid at 85 °C for 200 h. Theoretically, this glass can be used to seal wet Ta electrolytic capacitors. Differential scanning calorimetry (DSC) was used to analyze the glass transition temperature and thermal stability of borosilicate glasses. X-ray diffractometry (XRD), scanning electron microscopy (SEM), and Raman spectroscopy were used to study the microstructure of the amorphous phase of the borosilicate glass, which revealed a close relationship between the degree of network phase separation in the borosilicate glass and the degree of polymerization (isomorphic polyhedron value, IP) of the glass matrix. The IP value decreased from 3.82 to 1.98 with an increasing degree of phase separation. Boron transitions from [BO4] to [BO3] within the glass network structure with increasing boron oxide content, which diminishes the availability of free oxygen provided by alkaline oxide, resulting in a lower acid resistance. Notably, the glass exhibited optimal acid resistance at boron trioxide and mixed alkaline oxide contents of 15% and 6%, respectively. Raman experiments revealed how the distributions of various bridging oxygen atoms (Qn) affect the structural phase separation of the glass network. Additionally, Raman spectroscopy revealed the depolymerization of Q4 into Q3, thereby promoting high-temperature phase separation and highlighting the unique advantages of Raman spectroscopy for phase recognition.

Postsynthetically Modified Alkoxide-Exchanged Ni2(OR)2BTDD: Synergistic Interactions of CO2 with Open Metal Sites and Functional Groups.

Postsynthetic modifications (PSMs) of metal-organic frameworks (MOFs) play a crucial role in enhancing material performance through open metal site (OMS) functionalization or ligand exchange. However, a significant challenge persists in preserving open metal sites during ligand exchange, as these sites are inherently bound by incoming ligands. In this study, for the first time, we introduced alkoxides by exchanging bridging chloride in Ni2Cl2BTDD (BTDD=bis (1H-1,2,3,-triazolo [4,5-b],-[4',5'-i]) dibenzo[1,4]dioxin) through PSM. Rietveld refinement of synchrotron X-ray diffraction data indicated that the alkoxide oxygen atom bridges Ni(II) centers while the OMSs of the MOF are preserved. Due to the synergy of the existing OMS and introduced functional group, the alkoxide-exchanged MOFs showed CO2 uptakes superior to the pristine MOF. Remarkably, the tert-butoxide-substituted Ni_T exhibited a nearly threefold and twofold increase in CO2 uptake compared to Ni2Cl2BTDD at 0.15 and 1 bar, respectively, as well as high water stability relative to the other exchanged frameworks. Furthermore, the Grand Canonical Monte Carlo simulations for Ni_T suggested that CO2 interacts with the OMS and the surrounding methyl groups of tert-butoxide groups, which is responsible for the enhanced CO2 capacity. This work provides a facile and unique synthetic strategy for realizing a desirable OMS-incorporating MOF platform through bridging ligand exchange.

Postsynthetically Modified Alkoxide‐Exchanged Ni2(OR)2BTDD: Synergistic Interactions of CO2 with Open Metal Sites and Functional Groups

AbstractPostsynthetic modifications (PSMs) of metal–organic frameworks (MOFs) play a crucial role in enhancing material performance through open metal site (OMS) functionalization or ligand exchange. However, a significant challenge persists in preserving open metal sites during ligand exchange, as these sites are inherently bound by incoming ligands. In this study, for the first time, we introduced alkoxides by exchanging bridging chloride in Ni2Cl2BTDD (BTDD=bis (1H‐1,2,3,–triazolo [4,5‐b],–[4′,5′‐i]) dibenzo[1,4]dioxin) through PSM. Rietveld refinement of synchrotron X‐ray diffraction data indicated that the alkoxide oxygen atom bridges Ni(II) centers while the OMSs of the MOF are preserved. Due to the synergy of the existing OMS and introduced functional group, the alkoxide‐exchanged MOFs showed CO2 uptakes superior to the pristine MOF. Remarkably, the tert‐butoxide‐substituted Ni_T exhibited a nearly threefold and twofold increase in CO2 uptake compared to Ni2Cl2BTDD at 0.15 and 1 bar, respectively, as well as high water stability relative to the other exchanged frameworks. Furthermore, the Grand Canonical Monte Carlo simulations for Ni_T suggested that CO2 interacts with the OMS and the surrounding methyl groups of tert‐butoxide groups, which is responsible for the enhanced CO2 capacity. This work provides a facile and unique synthetic strategy for realizing a desirable OMS‐incorporating MOF platform through bridging ligand exchange.

Variations in proton transfer pathways and energetics on pristine and defect-rich quartz surfaces in water: Insights into the bimodal acidities of quartz

HypothesisUnderstanding the mechanisms of proton transfer on quartz surfaces in water is critical for a range of processes in geochemical, environmental, and materials sciences. The wide range of surface acidities (>9 pKa units) found on the ubiquitous mineral quartz is caused by the structural variations of surface silanol groups. Molecular scale simulations provide essential tools for elucidating the origin of site-specific surface acidities. SimulationsWe used density-functional tight-binding-based molecular dynamics combined with rare-event metadynamics simulations to probe the mechanisms of deprotonation reactions from ten representative surface silanol groups found on both pristine and defect-rich quartz (101) surfaces with Si vacancies. FindingsThe results show that deprotonation is a highly dynamic process where both the surface hydroxyls and bridging oxygen atoms serve as the proton acceptors, in addition to water. Deprotonation of embedded silanols through intrasurface proton transfer exhibited lower pKa values with less H-bond participation and higher energy barriers, suggesting a new mechanism to explain the bimodal acidity observed on quartz surface. Defect sites, recently shown to comprise a significant portion of the quartz (101) surface, diversify the coordination and local H-bonding environments of the surface silanols, changing both the deprotonation pathways and energetics, leading to a wider range of pKa values (2.4 to 11.5) than that observed on pristine quartz surface (10.4 and 12.1).

Hydrolysis mechanism of the cyclohexaborate anion: Unraveling the intricacies.

is a highly polymerized borate anion of three six-membered rings. Limited research on the hydrolysis mechanism under neutral solution conditions exists. Calculations based on density functional theory show that undergoes five steps of hydrolysis to form H3BO3 and . At the same time, there are a small number of borate ions with different degrees of polymerization during the hydrolysis process, such as triborate, tetraborate, and pentaborate anions. The structure of the borate anion and the coordination environment of the bridging oxygen atoms control the hydrolysis process. Finally, this work explains that in existing experimental studies, the reason for the low content in solution environments with low total boron concentrations is that it depolymerizes into other types of borate ions and clarifies the borate species. The conversion relationship provides a basis for identifying the possibility of various borate ions existing in the solution. This work also provides a certain degree of theoretical support for the cause of the "dilution to salt" phenomenon.

Quantum-Chemistry Study of the Hydrolysis Reaction Profile in Borate Networks: A Benchmark.

This investigation involved an ab initio and Density Functional Theory (DFT) analysis of the hydrolysis mechanism and energetics in a borate network. The focus was on understanding how water molecules interact with and disrupt the borate network, an area where the experimental data are scarce and unreliable. The modeled system consisted of two boron atoms, bridging oxygen atoms, and varying numbers of water molecules. This setup allows for an exploration of hydrolysis under different environmental conditions, including the presence of OH- or H+ ions to simulate basic or acidic environments, respectively. Our investigation utilized both ab initio calculations at the MP2 and CCSD(T) levels and DFT with a range of exchange-correlation functionals. The findings indicate that the borate network is significantly more susceptible to hydrolysis in a basic environment, with respect to an acidic or to a neutral pH setting. The inclusion of explicit water molecules in the calculations can significantly affect the results, depending on the nature of the transition state. In fact, some transition states exhibited closed-ring configurations involving water and the boron-oxygen-boron network; in these cases, there were indeed more water molecules corresponding to lower energy barriers for the reaction, suggesting a crucial role of water in stabilizing the transition states. This study provides valuable insights into the hydrolysis process of borate networks, offering a detailed comparison between different computational approaches. The results demonstrate that the functionals B3LYP, PBE0, and wB97Xd closely approximated the reference MP2 and CCSD(T) calculated reaction pathways, both qualitatively in terms of the mechanism, and quantitatively in terms of the differences in the reaction barriers within the 0.1-0.2 eV interval for the most plausible reaction pathways. In addition, CAM-B3LYP also yielded acceptable results in all cases except for the most complicated pathway. These findings are useful for guiding further computational studies, including those employing machine learning approaches, and experimental investigations requiring accurate reference data for hydrolysis reactions in borate networks.

Thermal Reactions of NiAl3O6+ and Al4O6+ with Methane: Reactivity Enhancement by Doping.

Investigation of the reactivity of heteronuclear metal oxide clusters is an important way to uncover the molecular-level mechanisms of the doping effect. Herein, we performed a comparative study on the reactions of CH4 with NiAl3O6+ and Al4O6+ cluster cations at room temperature to understand the role of Ni during the activation and transformation of methane. Mass spectrometric experiments identify that both NiAl3O6+ and Al4O6+ could bring about hydrogen atom abstraction reaction to generate CH3• radical; however, only NiAl3O6+ has the potential to stabilize [CH3] moiety and then transform [CH3] to CH2O. Density functional theory calculations demonstrate that the terminal oxygen radicals (Ot-•) bound to Al act as the reactive sites for the two clusters to activate the first C-H bond. Although the Ni atom cannot directly participate in methane activation, it can manipulate the electronic environment of the surrounding bridging oxygen atoms (Ob) and enable such Ob to function as an electron reservoir to help Ot-• oxidize CH4 to [H-O-CH3]. The facile reduction of Ni3+ to Ni+ also facilitates the subsequent step of activating the second C-H bond by the bridging "lattice oxygen" (Ob2-), finally enabling the oxidation of methane into formaldehyde. The important role of the dopant Ni played in improving the product selectivity of CH2O for methane conversion discovered in this study allows us to have a possible molecule-level understanding of the excellent performance of the catalysts doping with nickel.