Metal Oxide Sites Research Articles

Heteroatom Effect on Site-Selective Oxygen-Sulfur Substitution Reactions of Keggin-Type Polyoxotungstates.

Sulfur, a group 16 element, can substitute the oxygen sites of metal oxides, potentially providing them with unique properties and enabling new applications. Polyoxometalates (POMs) are anionic metal oxide clusters with wide structural diversity owing to arbitrary selection of their constituting metal atoms. However, substitution of the oxygen sites of POMs with sulfur atoms has been rarely explored. Recently, we reacted a Keggin-type POM [XW12O40]4- (IX; X = Si and Ge) with a sulfurizing reagent (Lawesson's reagent), synthesizing Keggin-type polyoxothiometalates (POTMs) [XW12O28S12]4- (IIX, X = Si and Ge) in which all 12 terminal oxygen atoms of IX were site-selectively substituted with sulfur atoms. Although the selected heteroatoms (X) and anion charges substantially influence the properties and reactivities of POMs, oxygen-sulfur substitution of Keggin-type POMs with other heteroatoms and anion charges has not been attempted. Herein, we report the oxygen-sulfur substitution reaction of Keggin-type POMs [XW12O40]n- (IX; X = Al, Si, and P; n = 5, 4, and 3, respectively) with various heteroatoms, yielding the corresponding Keggin-type POTMs [XW12O28S12]n- (IIX). The oxygen-sulfur substitution reaction depended on the heteroatom: POMs with higher anion charges reacted more strongly with the sulfurizing reagents. We also investigated the reaction mechanism of POMs and sulfurizing reagents.

Elusive supported surface M2Ox dimer active site (M = Re, W, Mo, Cr, V, Nb, and Ta)

Supported transition metal oxide catalysts are extensively used as heterogeneous catalysts for various energy, chemical, and environmental applications. The molecular structures of dehydrated surface metal oxide phases are crucial for understanding structure-activity/selectivity relationships that guide the design of enhanced catalysts. Some early studies suggested that dimeric (aka binuclear) surface metal oxide sites were more active/selective than monomeric (aka mononuclear) sites, prompting interest in synthesizing catalysts with supported dimeric metal oxide structures. This review examines the literature on dehydrated silica-based supported group 7-5 MOx catalysts (ReOx, WOx, MoOx, CrOx, VOx, NbOx, and TaOx on SiO2, MCM-41, AlOx/SiO2, and H-ZSM-5) for their surface metal oxide structures. In situ Raman, extended x-ray absorption fine structure, and ultraviolet-visible spectroscopy indicate that monomeric surface MOx structures predominate in all such catalysts. Therefore, the cursory use of dimeric surface M2Ox sites in catalytic mechanisms and reaction models in heterogeneous catalysis by supported metal oxides is questionable, and moving forward, the invoking of supporting dimeric surface M2Ox sites should be critically examined and backed up with direct spectroscopic methods.

Construction of "Metal Defect/Oxygen Defect Junction" in ZnFe2O4-NiCo2O4 Heterostructures for Enhancing Electrocatalytic Oxygen Evolution.

Defect engineering is a promising approach to improve the conductivity and increase the active sites of transition metal oxides used as catalysts for the oxygen evolution reaction (OER). However, when metal defects and oxygen defects coexist closely within the same crystal, their compensating charges can diminish the benefits of both defect structures on the catalyst's local electronic structure. To address this limitation, a novel strategy that employs the heterostructure interface of ZnFe2O4-NiCo2O4 to spatially separate the metal defects from the oxygen defects is proposed. This configuration positions the two types of defects on opposite sides of the heterojunction interface, creating a unique structure termed the "metal-defect/oxygen-defect junction". Physical characterization and simulations reveal that this configuration enhances electron transfer at the heterostructure interface, increases the oxidation state of Fe on the catalyst surface, and boosts bulk charge carrier concentration. These improvements enhance active site performance, facilitating hydroxyl adsorption and deprotonation, thereby reducing the overpotential required for the OER.

Electrochemically activated metal oxide sites at Rh–Ni2P electrocatalyst for efficient alkaline hydrogen evolution reaction

Electrochemically activated metal oxide sites at Rh–Ni2P electrocatalyst for efficient alkaline hydrogen evolution reaction

Phosphorus-modulated surface active center reconstruction in cerium oxide for polyols conversion into carbonates

Ionic liquids (ILs) can effectively regulate the surface morphology and acid-base sites of metal oxides, which is of great significance in the preparation of metal oxide nanomaterials. Here, cerium oxide (CeO2) was prepared in phosphonium-based ILs and P-doped CeO2 materials were obtained by doping phosphorous (P) on the surface of CeO2. Moreover, the yield and selectivity for ethylene carbonate (EC) synthesis catalyzed by CeO2 catalyst prepared were 77.26 % and 95.99 % respectively. The results indicated that an appropriate content of P could generate both Lewis acidic and basic sites related to P on the catalyst surface, and P-mediated frustrated Lewis acid-base pairs (FLPs) composed of P-OH as the basic center and Ce3+ as the acidic center was constructed. This work provides a new strategy for preparing novel CeO2 catalysts and regulating acid-base sites on the surface of that.

Enhancing Oxygen Evolution Reaction with Two-Dimensional Nickel Oxide on Au (111)

The nature of the active sites of transition metal oxides during the oxygen evolution reaction (OER) has attracted much attention. Herein, we constructed well-defined nickel oxide/Au (111) model catalysts to study the relationship between the structures and their OER activity using scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), electrochemical measurements, and density functional theory (DFT) calculations. The deposited nickel oxides on Au (111) were found to exhibit a two-dimensional (2D)/three-dimensional (3D) structure by regulating the annealing temperature. Combining STM, XPS and electrochemical measurements, our results demonstrated an optimal OER reactivity could be achieved for NiOx with a 2D structure on Au and provided a morphological description of the active phase during electrocatalysis.

Self-Supporting np-AlFeNiO Bifunctional Electrode Material for Electrochemical Water Splitting Prepared by Electrooxidation

Hydrogen production through water splitting is a promising path to develop renewable green energy. Effective, stable, and low-cost catalysts are the key to water splitting. In the present work, a series of self-supporting nanoporous alloys are prepared by using a dealloying process followed by electrooxidation. Among them, the np-AlFeNiO-4s sample exhibits remarkable activity (10 mA cm−2 at 32 mV for the HER and 278 mV for the OER) and good long-term stability (100 h) in alkaline conditions for both the HER and the OER. It only requires 1.56 V to reach 10 mA cm−2 current density for total water splitting performance. The very short time of electrooxidation can significantly improve the HER performance. Electrooxidation makes the metal and metal oxide sites on the electrode surface effectively coupled, which greatly enhances the kinetic rate of the Volmer and Heyrovsky steps. Appropriate electrooxidation is a rapid and easy way to improve the activity of the electrocatalyst, which has a broad application prospect in electrochemical water splitting.

Room-temperature sulfur doped NiMoO4 with enhanced conductivity and catalytic activity for efficient hydrogen evolution reaction in alkaline media

Transition metal oxides have been acknowledged for their exceptional water splitting capabilities in alkaline electrolytes, however, their catalytic activity is limited by low conductivity. The introduction of sulfur (S) into nickel molybdate (NiMoO4) at room temperature leads to the formation of sulfur-doped NiMoO4 (S-NiMoO4), thereby significantly enhancing the conductivity and facilitating electron transfer in NiMoO4. Furthermore, the introduction of S effectively modulates the electron density state of NiMoO4 and facilitates the formation of highly active catalytic sites characterized by a significantly reduced hydrogen absorption Gibbs free energy (ΔGH*) value of −0.09 eV. The electrocatalyst S-NiMoO4 exhibits remarkable catalytic performance in promoting the hydrogen evolution reaction (HER), displaying a significantly reduced overpotential of 84 mV at a current density of 10 mA cm−2 and maintaining excellent durability at 68 mA cm−2 for 10 h (h). Furthermore, by utilizing the anodic sulfide oxidation reaction (SOR) instead of the sluggish oxygen evolution reaction (OER), the assembled electrolyzer employing S-NiMoO4 as both the cathode and anode need merely 0.8 V to achieve 105 mA cm−2, while simultaneously producing hydrogen gas (H2) and S monomer. This work paves the way for improving electron transfer and activating active sites of metal oxides, thereby enhancing their HER activity.

Visualization of the Active Sites of Zinc-Chromium Oxides and the CO/H2 Activation Mechanism in Direct Syngas Conversion.

Despite wide studies demonstrating the versatility of the metal oxide-zeolite (OXZEO) catalyst concept to tackle the selectivity challenge in syngas chemistry, the active sites of metal oxides and the mechanism of CO/H2 activation remain to be elucidated. Herein, we demonstrate experimentally the role of Cr in zinc-chromium oxides and unveil visually, for the first time, the active sites for CO activation employing scanning transmission electron microscopy-electron energy loss spectroscopy using the volumetric density of surface carbon species as a descriptor. The ZnCr2O4 spinel surface with atomic ZnOx overlayer is the most active site for C-O bond dissociation, particularly at the narrow ZnCr2O4(110) facets constrained between the (311) and (111) facets, followed by the Cr-doped wurtzite ZnO surface. In comparison, the surfaces of ZnCr2O4 with aggregated ZnOx overlayers, pure ZnO, and the stoichiometric ZnCr2O4 exhibit a significantly lower activity. In situ synchrotron-based vacuum ultraviolet photoionization mass spectrometric study on different temperature programmed surface reactions with isotopes of C18O, 13CO, and D2 validates direct CO dissociation over ZnCrn oxides in CO, forming CH2 and further to hydrocarbons if H2 is present and CH2CO intermediates in syngas. The activity of CO dissociation and hydrogenation over ZnCrn oxides correlates well with the syngas-to-light-olefins activity of ZnCrn-SAPO-18 composite catalysts as a function of the Cr/Zn ratio.

Elucidation of C–N bond cleavage mechanism in quinoline hydrodenitrogenation over Pt-based catalysts

C–N bond breaking is a difficult but crucial step in the quinoline removal of coal-based liquids. Noble metal catalysts have higher C–N bond breaking activity, but their surface bond breaking mechanism is unclear. Atomic layer deposition creates more metal-oxide sites and generates different active species, which facilitates the mechanism study. For this reason, we used atomic layer deposition to deposit TiO2 on the catalyst surface and suggested a more complete C–N bond breaking mechanism in this study. The particle size and pore structure of the catalyst did not change significantly after the deposition, and the hydrogen adsorption was reduced when there were too many layers deposited and the surface Pt sites were occupied to a high degree. TiO2 is extremely susceptible to reduction to Ti3+ under hydrogen, and can change the nature of the electron density of Pt through oxygen vacancies, creating Ti3+-Ptδ− sites that are prone to protonation reactions. That means, the occurrence of these protonation reactions not only easily breaks the C–N bond, but also accelerates the rate of C–N bond cleavage due to the increased H coverage on the surface of the xcTi-PtAl catalysts. And the Ti3+-Ptδ− sites in catalyst had a stronger adsorption effect on the nitrogen-containing compounds, which in turn lowered the energy barriers of bond cleavage. It is concluded that protonation is a necessary step before the C–N bond can be broken. The subsequent steps were showed by the DFT calculations that the nitrogen-containing compounds adsorbed on the Ti3+-Ptδ− sites undergo β-H fracture after the protonation reaction, with the elimination reaction cleaving the C–N bond. The xcTi-PtAl catalysts by atomic layer deposition of Ti not only improve the C–N bond breaking performance, but also improve bond breaking stability by a factor of four compared to the Pt/Al2O3 catalysts.

Effective Enrichment of Phosphopeptides Using Magnetic Polyoxometalate-Based Metal-Organic Frameworks.

In this study, magnetic polyoxometalate-based metal-organic frameworks (Fe3O4-POMOFs) were designed and applied to the enrichment of phosphopeptides. Thanks to the abundant metal oxide and metal ion sites, the material had a strong affinity for phosphopeptides. Simultaneously, the high amount of amino and guanidyl groups provided hydrophilicity and positive charge for phosphopeptide capture. By coupling with MS detection, the established platform possessed good reusability, high sensitivity (0.01 fmol), and high selectivity (α-casein/β-casein/bovine serum albumin = 1:1:5000). Furthermore, the method was successfully used for the detection of phosphopeptides in nonfat milk, human serum, saliva, and A549 cell lysate, showing great potential for practical application.

Boosting specific capacitance of Mo-Co-(S,O) electrode via a synergistic optimization strategy

Low electrical conductivity and insufficient active sites of Co-based binary metal oxides or sulfides hamper their practical specific capacitance especially at high current densities. In the current work, we provide a novel synergistic optimization strategy including P doping and constant-current-charge activation (CA) to greatly improve the specific capacitance of sulfur and oxygen-containing Mo-Co binary compounds (Mo-Co-(S,O)) electrode. The synergistic effect of the P doping and activation not only increases the electrical conductivity but also improves the electroactive sites. As a result, the optimized Mo-Co-(S,O)/P-CA electrode shows exceptional specific capacitance (∼9.64 F cm−2/2931 F g−1 at 12.5 mA cm−2), approximately 20 times the pristine Mo-Co-(S,O). Moreover, an asymmetric supercapacitor prepared with Mo-Co-(S,O)/P-CA cathode and conductive carbon cloth achieves a high energy density of 0.61 mWh cm−2 at a power density of 4.25 mW cm−2, and outstanding cyclic performance with 121.6% of capacitance retention after 12,000 cycles.

Rapid synthesis of MgCo2O4: Morphology control, defect modulation, activity enhancement and applications

Organic fuels are the main factors affecting the morphology, pore structure and catalytic active sites of metal oxides in solution combustion synthesis (SCS). However, due to the diversity of organic fuel structures, the specific role of organic fuel types on SCS is questionable. In this work, we compared the effects of five organic fuels on the thermocatalytic active sites of graded porous MgCo2O4 nanomaterials. MgCo2O4 (CA-MCO) prepared with citric acid as fuel has the largest specific surface area and the richest pore structure with the largest number of active sites. And the porous CA-MCO exhibited the best catalytic properties that the THTD of AP decreased by 206.06 °C, the activation energy (Ea) decreased by 104.58 kJ·mol−1, and the reaction rate (k) increased by 2.49 s−1. A possible catalytic mechanism for the thermal decomposition of AP was also proposed based on TG-MS and Hall effect tests. Finally, CA-MCO was applied to AP/HTPB-based composite solid propellants (CSPs), and the results showed that the introduction of CA-MCO significantly shortened the ignition delay time of the CSPs (From 29 ms to 8 ms), indicating its potential application in the CSPs.

Physico-Chemical Modifications Affecting the Activity and Stability of Cu-Based Hybrid Catalysts during the Direct Hydrogenation of Carbon Dioxide into Dimethyl-Ether.

The direct hydrogenation of CO2 into dimethyl-ether (DME) has been studied in the presence of ferrierite-based CuZnZr hybrid catalysts. The samples were synthetized with three different techniques and two oxides/zeolite mass ratios. All the samples (calcined and spent) were properly characterized with different physico-chemical techniques for determining the textural and morphological nature of the catalytic surface. The experimental campaign was carried out in a fixed bed reactor at 2.5 MPa and stoichiometric H2/CO2 molar ratio, by varying both the reaction temperature (200-300 °C) and the spatial velocity (6.7-20.0 NL∙gcat-1∙h-1). Activity tests evidenced a superior activity of catalysts at a higher oxides/zeolite weight ratio, with a maximum DME yield as high as 4.5% (58.9 mgDME∙gcat-1∙h-1) exhibited by the sample prepared by gel-oxalate coprecipitation. At lower oxide/zeolite mass ratios, the catalysts prepared by impregnation and coprecipitation exhibited comparable DME productivity, whereas the physically mixed sample showed a high activity in CO2 hydrogenation but a low selectivity toward methanol and DME, ascribed to a minor synergy between the metal-oxide sites and the acid sites of the zeolite. Durability tests highlighted a progressive loss in activity with time on stream, mainly associated to the detrimental modifications under the adopted experimental conditions.

Steering the reaction pathway of syngas-to-light olefins with coordination unsaturated sites of ZnGaOx spinel

Significant progress has been demonstrated in the development of bifunctional oxide-zeolite catalyst concept to tackle the selectivity challenge in syngas chemistry. Despite general recognition on the importance of defect sites of metal oxides for CO/H2 activation, the actual structure and catalytic roles are far from being well understood. We demonstrate here that syngas conversion can be steered along a highly active and selective pathway towards light olefins via ketene-acetate (acetyl) intermediates by the surface with coordination unsaturated metal species, oxygen vacancies and zinc vacancies over ZnGaOx spinel−SAPO-34 composites. It gives 75.6% light-olefins selectivity and 49.5% CO conversion. By contrast, spinel−SAPO-34 containing only a small amount of oxygen vacancies and zinc vacancies gives only 14.9% light olefins selectivity at 6.6% CO conversion under the same condition. These findings reveal the importance to tailor the structure of metal oxides with coordination unsaturated metal sites/oxygen vacancies in selectivity control within the oxide-zeolite framework for syngas conversion and being anticipated also for CO2 hydrogenation.

Single-Atom Metal Oxide Sites as Traps for Charge Separation in the Zirconium-Based Metal–Organic Framework NDC–NU-1000

Single-Atom Metal Oxide Sites as Traps for Charge Separation in the Zirconium-Based Metal–Organic Framework NDC–NU-1000

Enhancing electrochemical performance of electrode material via combining defect and heterojunction engineering for supercapacitors

The poor conductivity and deficient active sites of transition metal oxides lead to low energy density of supercapacitors, which limits their wide application. In this work, double transition metal oxide heterojunctions with oxygen vacancy (Vo-ZnO/CoO) nanowires are prepared by effective hydrothermal and thermal treatments. The formation of the heterojunction results in the redistribution of interface charge between ZnO and CoO, generating an internal electric field to accelerate the electron transport. Meanwhile, oxygen vacancies can enhance the redox reaction activity to further improve the electrochemical kinetics of the electrode material. Therefore, the prepared Vo-ZnO/CoO can provide a superior specific capacity of 845 C g−1 (1 A g−1). An asymmetric supercapacitor with the Vo-ZnO/CoO as positive electrode shows a higher energy density of 51.6 Wh kg−1 when the power density reaches 799.9 W kg−1. This work proposes a synergistic combination of defect and heterojunction engineering to improve the electrochemical properties of materials, providing an important guidance for material design in energy-storage field.

Proton-beam engineered surface-point defects for highly sensitive and reliable NO2 sensing under humid environments

Cross-interference with humidity is a major limiting factor for the accurate detection of target gases in semiconductor metal-oxide gas sensors. Under humid conditions, the surface-active sites of metal oxides for gas adsorption are easily deactivated by atmospheric water molecules. Thus, development of a new approach that can simultaneously improve the two inversely related features for realizing practical gas sensors is necessary. This paper presents a facile method to engineer surface-point defects based on proton-beam irradiation. The sensor irradiated with a proton beam shows not only an improved NO2 response but also considerable tolerance toward humidity. Based on surface analyses and DFT calculations, it is found that proton beams induce three types of point defects, which make NO2 molecules preferentially adsorb on the ZnO surfaces compared to H2O molecules, eventually enabling improved NO2 detection with less humidity interference.

Fabrication of tantalum oxyfluoride and oxynitride thin films via ammonolysis of sol–gel processed tetraethoxo (β-diketonato) tantalum (V) precursors for enhanced photocatalytic activity

In the present report, the generation of Tantalum oxyfluoride and oxynitride upon ammonolysis of the gel obtained from modified tantalum-alkoxo complexes is reported. To the best of our knowledge, this is the first report of the formation of tantalum oxyfluoride thin films via ammonolysis of the β-diketone modified tantalum-alkoxo complex [Ta(OEt)4(CF3COCH2COCH3)]m. The integration of nitrogen and fluorine in lattice sites of metal oxides leads to significant reduction in the bandgap, resulting in their activation under visible light. Moreover, in this report the effect of the modified alkoxide precursors and ammonolysis on the photophysical properties of Ta2O5 thin films have also been investigated and compared with the results obtained from films fabricated from unmodified tantalum (V) ethoxide. 1H NMR, 13C NMR and elemental analyses confirmed successful modification of tantalum (V) ethoxide to [Ta(OCH2CH3)4(CH3COCHClCOCH3)]m (1), [Ta(OCH2CH3)4(CF3COCH2COCH3]m (2) and [Ta(OCH2CH3)4 (CH3COC(CH3)2COCH3))]m (3). The fabrication of Ta2O5 thin films involved the spin casting of the gels of modified tantalum alkoxo complexes (processed by sol–gel method) on to glass substrate. X-ray photoelectron spectroscopy results show that nitrogen was incorporated into the ammonolyzed films fabricated from complex precursors (1) and (3), while the presence of fluorine as tantalum oxyfluoride was confirmed in the ammonolyzed film fabricated from complex (2) precursor. The optical characterization insinuate bandgap narrowing from 3.55 eV for undoped film prepared from tantalum (V) ethoxide to 3.47 eV for undoped film prepared from [Ta(OEt)4(CF3COCH2COCH3)]m and 3.05 eV for ammonolyzed film obtained from [Ta(OEt)4(CF3COCH2COCH3)]m precursor. Furthermore, enhanced photocatalytic efficiency of the films is demonstrated by degradation of methylene blue dye.

Detailed Mechanism of Ethanol Transformation into Syngas on Catalysts Based on Mesoporous MgAl2O4 Support Loaded with Ru + Ni/(PrCeZrO or MnCr2O4) Active Components

Mechanism of ethanol partial oxidation into syngas over catalysts based on mesoporous MgAl2O4 spinel loaded with fluorite PrCeZrO or spinel MnCr2O4 oxides and promoted by Ru + Ni was studied by in situ FTIRS and 18O SSITKA. Surface species (ethoxy, adsorbed ethanol, acetaldehyde, acetate, etc.) were identified and their thermal stability and reactivity were estimated. Analysis of kinetics of the 18O transfer into reaction products (CO, CO2, CH3CHO) allowed to estimate the rates of steps and present a scheme of the reaction mechanism including (1) fast CH3CHO formation on mixed metal oxide sites; (2) rate-limiting stage of surface oxygen species incorporation into acetaldehyde or ethoxy species with C–C bond rupture yielding CO and CO2 along with H2 and H2O; (3) water gas shift reaction by redox mechanism affecting CO/CO2 ratio and their oxygen isotope fraction. Strong interaction of PrCeZrO or MnCr2O4 oxides with MgAl2O4 support results in decreasing constants of main reaction steps in comparison with those for catalysts based on bulk fluorite and spinel oxides, correlating with a higher surface oxygen bonding strength and its low coverage revealed by pulse microcalorimetry. DFT analysis confirmed a low energy barrier of the step of Ru–O oxygen incorporation into C–C bond of ethoxy species with its rupture explaining a higher syngas selectivity for Ru-doped catalysts.