Oxide Support Research Articles

Enhancing methane formation in carbon dioxide hydrogenation on nickel clusters with zirconium additives: Exploring active sites, reaction pathways, and catalytic mechanisms

This study focuses on the catalytic reaction of carbon dioxide (CO2) hydrogenation using 0.5 wt% nickel (Ni) deposited on silica oxide support (SiO2). Initially, these Ni clusters exhibit limited catalytic activity and selectivity toward carbon monoxide (CO) formation. However, the introduction of zirconium ions (Zr4+) onto the Ni clusters leads to a remarkable improvement in the catalytic efficiency of CO2 hydrogenation and methane (CH4) production. The interaction between Ni and ZrO2 generates interfacial sites that play a multifaceted role. These sites facilitate the binding of acidic CO2 and promote the atomic hydrogen migration from ZrO2 to Ni. Consequently, the creation of interfacial sites on the Ni catalysts directly enhances the rate of CO2 hydrogenation while also increasing CH4 selectivity. The primary intermediate in this process appears to be monodentate formate species, which can undergo direct decomposition to CO or conversion into formic acid intermediates. The formic acid intermediates subsequently undergo hydrogenation, ultimately leading to the production of CH4.

Periodic open cellular structures (POCS) as catalyst support for intensified heat transport in the partial oxidation of methanol to formaldehyde

Heat transport in catalytic reactors is one of the most important factors in reactor design, especially for highly endo- or exothermic reactions. The limited thermal conductivity of randomly packed beds can be significantly improved when alternative catalyst supports are used. A new generation thereof are periodic open cellular structures (POCS), which are used in this study as catalyst support for the partial oxidation of methanol to formaldehyde, an exothermic gas phase reaction. A comparison to traditional packed bed reactors revealed that a POCS made of the highly conductive alloy AlSi10Mg can significantly reduce the hot-spot temperature, allowing almost isothermal operation at optimal reaction conditions. The improved temperature control allows for operation with higher methanol inlet concentrations and wall temperatures as compared to the commercial process. The beneficial heat transport properties of POCS were used to conduct isothermal kinetic measurements at elevated temperature. Based on these findings and the design freedom of additive manufacturing, an optimized cellular structure was designed and fabricated, which improved the heat transport especially in the critical inlet section of the reactor.

Ni-Mo bimetallic oxides/rGO nanocomposites as counter electrode for the application of DSSCs

The one-pot chemical reduction process was used to generate the bimetallic Ni–Mo nanoparticles attached to reduced graphene oxide (rGO) nanocomposite, which was then used as an effective counter electrode in dye-sensitized solar cells (DSSC). Diffraction patterns were used to investigate the face-centered crystalline structure of the spherical-shaped Ni–Mo nanoparticles that were uniformly anchored over the surface of rGO. The nanoparticles had an average diameter ranging from 70 to 120 nm. Raman spectroscopy was utilized to investigate the structural interaction that was created by the presence of bimetallic nanoparticles and the graphene oxide support. In addition, the rGO/Ni–Mo counter electrode equipped DSSC demonstrated the highest solar to electrical energy conversion efficiency of 3.11% under irradiation from one sun with a fill factor (FF) of 0.48.

Mechanochemistry: A Green and Fast Method to Prepare a New Generation of Metal Supported Catalysts

In this review, we report on recent advances in the use of mechanochemistry to synthesise new catalytic materials. We report recent results obtained by our groups where a rational design of the milling parameters led to the synthesis of advanced materials with novel properties such as unconventional arrangements of metals on the surface of oxide support materials, highly dispersed metals or the stabilisation of species in particular oxidation states. These properties resulted in superior catalytic performances of the mechanochemically-synthesised catalysts compared to their counterparts prepared by traditional impregnation methods. To illustrate these advances, we review the progress made in two important fields of catalysis where noble metals are used: (i) emission control catalysis using palladium-based materials; (ii) the development of photocatalysts to produce hydrogen based on gold and palladium materials.

Mechanism on CMD reaction regulated by supports and promoters of Fe-based catalysts

Methane cracking technology for low-carbon energy conversion to produce hydrogen is a key technical approach in the pursuit of fossil energy decarbonization. Catalytic methane decomposition (CMD) is a process that accomplishes the fundamental removal of carbon from fossil energy without oxygen, producing high-quality carbon-based materials and H2. The functionality of supports and promoters was investigated using inorganic metal oxide support Al2O3, supported active metal Fe, and cocatalyst K. The results show that the Al2O3–Fe catalyst achieves the highest CH4 conversion of 65% at 850 °C, with a gas-phase H2 yield of 1189.72 mmol/gFe within 3 h, and a solid-phase carbon yield of 6.32 g/gFe, significantly higher than at 750 °C. The Al2O3–Fe–K catalyst achieves a methane conversion rate of 66.28% at 850 °C for 1.5 h, exhibiting relatively fast deactivation. The Al2O3–Fe catalyst catalyzes the formation of carbon nanotubes (CNTs) through methane cracking, resulting in mainly 'chain-locked' morphology. The promoter K acts on the surrounding metal clusters to influence the dispersion of active metal. The Al2O3–Fe–K catalyst is more favorable for the production of 'bamboo-shaped' carbon nanotubes, suggesting that K has a more significant impact on shaping the CNTs' products.

Influence of the oxidic support material on the platinum-catalyzed benzyl alcohol oxidation

Influence of the oxidic support material on the platinum-catalyzed benzyl alcohol oxidation

The Effect of Reduction Pretreatments on the Size of Supported Pt and Pd Nanoparticles Prepared by Strong Electrostatic Adsorption

Supported catalyst synthesis involves pretreatment (drying, reduction) of metal complexes to form metal nanoparticles. This study has been undertaken to explore the effect of reduction temperature, heating rate, and water partial pressure on final particle size of Pt and Pd supported on a total of four carbon and oxide supports. Supported nanoparticles were synthesized by strong electrostatic adsorption (SEA) and dry impregnation (DI); the former method was hypothesized to yield greater nanoparticle stability in thermochemical reducing environments stemming from the strong interaction of the precursor with the support during impregnation. Reduced samples were characterized by in-situ and ex-situ XRD and STEM. The DI-derived samples generally showed an expected increase of particle size with increased reduction temperature, and severe particle coalescence in humid hydrogen, while the SEA-derived samples did not sinter at the elevated reduction temperatures (up to 500 °C) and were remarkably stable in the humid reducing environment.Graphical

Insight into the role of metal support interface through the synergistic effect between Ag and α-Bi2Mo3O12 support for the selective oxidation of propylene to acrolein

Pre-synthesized morphologically tailored size and shape selective silver nanoparticles (AgNPs) decorated on bismuth molybdate support (AgNPs/α–Bi2Mo3O12) using simple wet impregnation method was employed. The prepared AgNPs/α-Bi2Mo3O12 nanocatalysts were tested in the selective partial oxidation of propylene to acrolein reaction. The introduction of well-defined size and shape of AgNPs on α–Bi2Mo3O12 is greatly promoted the strong metal support interactions (SMSI), creation of oxygen vacancies (Ov) and high propylene adsorption binding energy (calculated by DFT). The strong metal support interactions between Ag and α-Bi2Mo3O12 is clearly elucidated by the high quality HRTEM and STEM–HAADF microscopic images. In addition, surface atomic molar ratio measured by XPS analysis determined the key redox properties of AgNPs/α–Bi2Mo3O12 system and their influence on the overall catalytic efficiency in the oxidation of propylene via reduction of Mo6+ to Mo5+ initiated at low temperatures in Ag/α–Bi2Mo3O12 system. The Mo reduction is further confirmed by the activated oxygen removal from the MoO42– moieties after Ag incorporation on α–Bi2Mo3O12. Thus, confirmed the oxidation reaction pathway follows a Mars–van–Krevelen process. Further, DFT calculations supported the propylene adsorption is more favorable over Ag/α–Bi2Mo3O12 than bare α–Bi2Mo3O12 support. The propylene oxidation performance over Ag/α–Bi2Mo3O12 system was 5.5 times higher than bare α–Bi2Mo3O12 support, probably due to an enabled strong metal support interaction and increased oxygen vacancies.

Ex situ and in situ studies on structural features of Pt/Ce0.75Zr0.25O2 catalyst for water gas shift reaction

Pt/Ce1-xZrxO2 catalysts have shown high activity in water gas shift (WGS) reaction, but their structural organization has been studied insufficiently. This work represents a detailed structural study on the supported Pt species and the metal/support interface in a 5 wt% Pt/Ce0.75Zr0.25O2 catalyst in the initial state, after reductive activation, and after WGS reaction in H2-enriched reformate-simulating mixture. A wide range of methods was used: ex situ and in situ X-ray diffraction (XRD) studies, high resolution transmission electron microscopy (HRTEM), X-ray atomic pair distribution function (PDF) method, pseudo in situ X-ray photoelectron spectroscopy (XPS), hydrogen temperature-programmed reduction (H2-TPR). The Ce0.75Zr0.25O2 mixed oxide was shown to provide a highly dispersed state of Pt species. XPS revealed that the initial catalyst contains Pt2+species. PDF analysis allowed us to propose the structure of ultrafine PtO particles and to elucidate the metal-support interaction with fixation of Pt ions on the support surface. In situ XRD, pseudo in situ XPS, and H2-TPR studies revealed the reduction of ultrafine PtO particles in H2 atmosphere at low temperatures (20–90°С) with the formation of metallic Pt0 particles and simultaneous partial reduction of the support surface due to the hydrogen spillover. Catalytic tests of the as-prepared and poisoned with chlorine 5wt% Pt/Ce0.75Zr0.25O2 catalysts in the WGS reaction showed an important role of the oxygen vacancies in the oxide support as active sites. These findings contribute to the understanding catalytic performance of Pt/Ce1-xZrxO2 systems.

Promoted Ni Catalyst Over Titania-Zirconia Support for Partial Oxidation of Methane: Simple and Practical Catalysts

Promoted Ni Catalyst Over Titania-Zirconia Support for Partial Oxidation of Methane: Simple and Practical Catalysts

Reductive Segregation During the Synthesis of Sb−SnO2-Supported Iridium Electrocatalysts for the Oxygen Evolution Reaction

A metal-organic chemical deposition approach using an Ir(acac)3 precursor was employed to synthesise oxide−supported iridium-based electrocatalysts for the oxygen evolution reaction (OER) in acidic media. Inert and oxidising deposition conditions were explored in two temperature regimes, and the influence of these parameters on the physicochemical and electrochemical properties of catalysts consisting of IrOx supported on Sb–SnO2 (ATO) were studied. Surprisingly, it was found that increasing the deposition temperature up to 620 °C favoured the formation of reduced iridium phases even in the presence of an oxidising reaction environment. This was explained by a thermodynamic preference for reduced phases at high temperatures, as well as the presence of acetylacetonate ligand decomposition products serving as reducing agents. Similarly, the reductive segregation of Sb from the ATO support at high temperatures leads to the loss of conductivity of the support, and the formation of Ir–Sb–Sn alloyed nanoparticles. These processes resulted in a loss of OER performance for the materials prepared under high-temperature conditions. Our findings highlight the importance of carefully selecting the temperature range during the synthesis of oxidic support materials and electrocatalysts for the OER.

Fundamental Structural and Electronic Understanding of Palladium Catalysts on Nitride and Oxide Supports.

The nature of the support can fundamentally affect the function of a heterogeneous catalyst. For the novel type of isolated metal atom catalysts, sometimes referred to as single-atom catalysts, systematic correlations are still rare. Here, we report a general finding that Pd on nitride supports (non-metal and metal nitride) features a higher oxidation state compared to that on oxide supports (non-metal and metal oxide). Through thorough oxidation state investigations by X-ray absorption spectroscopy (XAS), X-ray photoelectron spectroscopy (XPS), CO-DRIFTS, and density functional theory (DFT) coupled with Bader charge analysis, it is found that Pd atoms prefer to interact with surface hydroxyl group to form a Pd(OH)x species on oxide supports, while on nitride supports, Pd atoms incorporate into the surface structure in the form of Pd-N bonds. Moreover, a correlation was built between the formal oxidation state and computational Bader charge, based on the periodic trend in electronegativity.

Fundamental structural and electronic understanding of palladium catalysts on nitride and oxide supports

The nature of the support can fundamentally affect the function of a heterogeneous catalyst. For the novel type of isolated metal atom catalysts, sometimes referred to as single‐atom catalysts, systematic correlations are still rare. Here, we report a general finding that Pd on nitride supports (non‐metal and metal nitride) always features a higher oxidation state compared to that on oxide supports (non‐metal and metal oxide). Through thorough oxidation state investigations by X‐ray absorption spectroscopy (XAS), X‐ray photoelectron spectroscopy (XPS), CO‐DRIFTS, and density functional theory (DFT) coupled with Bader charge analysis, it is found that Pd atoms prefer to interact with surface hydroxyl group to form a Pd(OH)x species on oxide supports, while on nitride supports, Pd atoms incorporate into the surface structure in the form of Pd−N bonds. Moreover, a correlation was built between the formal oxidation state and the computational Bader charge, based on the periodic trend in electronegativity.

Growth of copper-nickel (Cu-Ni) dual atom catalysts over graphene variants as active anodes for clean oxygen generation: Integrative experimental and computational validation

The development of atomically precise metals on the surface of graphene has led to superior electrocatalytic properties for the clean oxygen production. In this study, Cu single-atom and NiCu dual-atom catalysts supported on different graphene variants were effectively developed as electrocatalysts for the production of clean oxygen. Various techniques, including XRD, SEM, Raman, HR-TEM, EXAFS and XPS, were used to characterize these synthesized electrocatalysts. The extent of reduction in graphene oxide (GO) support was confirmed using Raman analysis which demonstrated a greater ID/IG-apparent intensity ratio, indicating that the GO (ID/IG=0.9) has more sp3-hybridized carbon with respect to the rGO (ID/IG= 0.6). The HR-TEM analysis with EDX and STEM data confirmed the dispersion of Cu and NiCu dimer over the surface of graphene variants. XPS and EXAFS studies revealed predominant metallic nature of Cu and NiCu dimer with the synergistic interplay between the constituent atoms. Copper-nickel dimer catalyst supported on reduced graphene oxide (CuNi/rGO) demonstrated the best electrocatalytic performance, where a lower overpotential of 320 mV was observed to reach a current density of 10 mA cm−2 with lowest Tafel slope of 110 mV/dec for oxygen evolution reaction. Good stability was observed after 1000 CV cycles and 50 h of electrolysis in 1.0 M KOH electrolytic solution at an oxidation potential of 1.62 V (vs RHE). Control experiments were also performed using borosilicate pyrex glass and Teflon made electrochemical cells in order to over rule the probable involvement of leached out impurities in OER reaction under extreme alkaline conditions. The calculations obtained from Density Functional Theory (DFT) suggest that the dual-atom catalysts have lower overpotential (0.33 V at Cu-site) with respect to the single-atom catalysts, which agreed well with the experimental results. Also, the Cu-site OER was found to have lower overpotential (0.33 V) than the Ni-site (0.47 V). Thus, this study can provide valuable insights into developing low-cost dual-atom electrocatalysts, where the synergism between constituent elements in the dimer and their stabilization by graphene matrix can be exploited for various electrochemical reactions.

Constructing Efficient CuO-Based CO Oxidation Catalysts with Large Specific Surface Area Mesoporous CeO2 Nanosphere Support.

CeO2 is an outstanding support commonly used for the CuO-based CO oxidation catalysts due to its excellent redox property and oxygen storage-release property. However, the inherently small specific surface area of CeO2 support restricts the further enhancement of its catalytic performance. In this work, the novel mesoporous CeO2 nanosphere with a large specific surface area (~190.4 m2/g) was facilely synthesized by the improved hydrothermal method. The large specific surface area of mesoporous CeO2 nanosphere could be successfully maintained even at high temperatures up to 500 °C, exhibiting excellent thermal stability. Then, a series of CuO-based CO oxidation catalysts were prepared with the mesoporous CeO2 nanosphere as the support. The large surface area of the mesoporous CeO2 nanosphere support could greatly promote the dispersion of CuO active sites. The effects of the CuO loading amount, the calcination temperature, mesostructure, and redox property on the performances of CO oxidation were systematically investigated. It was found that high Cu+ concentration and lattice oxygen content in mesoporous CuO/CeO2 nanosphere catalysts greatly contributed to enhancing the performances of CO oxidation. Therefore, the present mesoporous CeO2 nanosphere with its large specific surface area was considered a promising support for advanced CO oxidation and even other industrial catalysts.

Electron transfer enhanced catalytic activity of nitrogen doped reduced graphene oxide supported CuCo2O4 towards the fast reduction of 4-nitrophenol in water

There has been a growing interest in the design and development of graphene based composite materials with superior performances for environmental catalytic applications. But in most of the studies the synthesis conditions require elevated temperatures and expensive working setups (high temperature furnaces, autoclaves, inert atmosphere conditions etc.). In this reported work, the nitrogen doped reduced graphene oxide supported CuCo2O4 (NG/CuCo2O4) composites were prepared through a simple one pot synthesis method under mild conditions (∼95 °C and air atmosphere) and successfully employed as catalysts for the reduction of toxic 4-nitrophenol (4NP). The characterization results revealed the successful formation of NG/CuCo2O4 composites with a possible charge transfer interaction between nitrogen doped reduced graphene oxide support of CuCo2O4. The NG/CuCo2O4 hybrids exhibited robust catalytic activity in 4NP reduction with an activity factor of 261.5 min−1 g−1. A 4NP conversion percentage which is as high as 99.5% was achieved within 11 min using the NG/CuCo2O4 catalyst. The detailed kinetic analysis confirmed the Langmuir-Hinshelwood model for the NG/CuCo2O4 catalysed 4NP reduction. The nitrogen doped reduced graphene oxide support modified the electronic levels of CuCo2O4 nanoparticles through electron transfer interactions and enhanced the catalytic activity of CuCo2O4 in NG/CuCo2O4 through improved adsorption of reactant ions and effective generation of active hydrogen species. The good reusability and stability along with profound activity of NG/CuCo2O4 catalyst makes it a promising material for wide scale catalytic applications.

NMR Spectroscopic Signatures of Cationic Surface Sites from Supported Coinage Metals Interacting with N-Heterocyclic Carbenes.

N-heterocyclic carbenes (NHCs) have been extensively studied to modulate the reactivity of molecular catalysts, colloids, and their supported analogues, being isolated sites, clusters, or nanoparticles. While the interaction of NHCs on metal surfaces has been discussed in great detail, showing specific coordination chemistry depending on the type of NHC ligands, much less is known when the metal is dispersed on oxide supports, as in heterogeneous catalysts. Herein, we study the interaction of NHC ligands with Au surface sites dispersed on silica, a nonreducible oxide support. We identify the easy formation of bis-NHC ligated Au(I) surface sites parallel to what is found on metallic Au surfaces. These species display a specific 13C NMR spectroscopic signature that clearly distinguishes them from the mono-NHC Au(I) surface sites or supported imidazoliums. We find that bis-ligated surface species are not unique to supported Au(I) species and are found for the corresponding Ag(I) and Cu(I) species, as well as for the isolobal surface silanols. Furthermore, the interaction of NHC ligand with silica-supported Au nanoparticles also yields bis-NHC ligated Au(I) surface sites, indicating that metal atoms can also be easily extracted from nanoparticles, further illustrating the dynamics of these systems and the overall favorable formation of such bis-ligated species across a range of systems, besides what has been found on crystalline metal facets.

Determination of local fractal dimension of the catalyst support MgAl2O4 surface

In this paper, a procedure for estimating local fractal dimensionality values for greyscale images was developed. This procedure was tested on synthesised fractal and multifractal Brownian surfaces. The use of the method of detrended fluctuation analysis to determine the Hurst index for samples with a size not exceeding 2000 points was analysed. The optimal values of the sample size and the scale parameter have been obtained, allowing the Hurst index to be calculated with an error of less than 20%. The procedure was also tested on greyscale images, which are 8-bit representations of a synthesised fractal surface. The peculiarities of the application of the procedure for calculating the local fractal dimension for images obtained by scanning electron microscopy have been analysed. The values of the local fractal dimension of the oxide support MgAl2O4 are calculated using SEM images at different magnifications. It has been shown that, taking into account the fractal dimensionality calculation, different morphologies of the particle surface are observed at different scales of image magnification. At the highest magnification, the particle surface is found to consist of embedded smooth micron particles. The surface morphology of the MgAl2O4 particle depends on the micro- and mesopores between the embedded particles, this surface can be characterised by a fractal surface with FD2 = 2.3–2.4.

Supported Platinum Nanoparticles Catalyzed Carbon-Carbon Bond Cleavage of Polyolefins: Role of the Oxide Support Acidity.

Supported platinum nanoparticle catalysts are known to convert polyolefins to high-quality liquid hydrocarbons using hydrogen under relatively mild conditions. To date, few studies using platinum grafted onto various metal oxide (MxOy) supports have been undertaken to understand the role of the acidity of the oxide support in the carbon-carbon bond cleavage of polyethylene under consistent catalytic conditions. Specifically, two Pt/MxOy catalysts (MxOy = SrTiO3 and SiO2-Al2O3; Al = 3.0 wt %, target Pt loading 2 wt % Pt ∼1.5 nm), under identical catalytic polyethylene hydrogenolysis conditions (T = 300 °C, P(H2) = 170 psi, t = 24 h; Mw = ∼3,800 g/mol, Mn = ∼1,100 g/mol, Đ = 3.45, Nbranch/100C = 1.0), yielded a narrow distribution of hydrocarbons with molecular weights in the range of lubricants (Mw = < 600 g/mol; Mn < 400 g/mol; Đ = 1.5). While Pt/SrTiO3 formed saturated hydrocarbons with negligible branching, Pt/SiO2-Al2O3 formed partially unsaturated hydrocarbons (<1 mol % alkenes and ∼4 mol % alkyl aromatics) with increased branch density (Nbranch/100C = 5.5). Further investigations suggest evidence for a competitive hydrocracking mechanism occurring alongside hydrogenolysis, stemming from the increased acidity of Pt/SiO2-Al2O3 compared to Pt/SrTiO3. Additionally, the products of these polymer deconstruction reactions were found to be independent of the polyethylene feedstock, allowing the potential to upcycle polyethylenes with various properties into a value-added product.

Confinement-Induced Indium Oxide Nanolayers Formed on Oxide Support for Enhanced CO2 Hydrogenation Reaction.

An enclosed nanospace often shows a significant confinement effect on chemistry within its inner cavity, while whether an open space can have this effect remains elusive. Here, we show that the open surface of TiO2 creates a confined environment for In2O3 which drives spontaneous transformation of free In2O3 nanoparticles in physical contact with TiO2 nanoparticles into In oxide (InOx) nanolayers covering onto the TiO2 surface during CO2 hydrogenation to CO. The formed InOx nanolayers are easy to create surface oxygen vacancies but are against over-reduction to metallic In in the H2-rich atmospheres, which thus show significantly enhanced activity and stability in comparison with the pure In2O3 catalyst. The formation of interfacial In-O-Ti bonding is identified to drive the In2O3 dispersion and stabilize the metastable InOx layers. The InOx overlayers with distinct chemistry from their free counterpart can be confined on various oxide surfaces, demonstrating the important confinement effect at oxide/oxide interfaces.