Non-reducible Support Research Articles

Anchoring PdOx clusters on defective alumina for improved catalytic methane oxidation

Evolution of the Pd active centers in size and spatial distribution leads to an irreversible deactivation in many high-temperature catalytic processes. This research demonstrates the use of a defective alumina (Al2O3-x) as catalyst support to anchor Pd atoms and suppress the growth of Pd clusters in catalytic methane oxidation. A combination of operando spectroscopy and density functional theory (DFT) calculations provide insights into the evolution of Pd species and reveals distinct catalytic methane oxidation mechanisms on Pd single atoms, clusters, and nanoparticles (NPs). Among these Pd species, the cluster active centers are found to be the most favorable participants in methane oxidation due to their high dispersion, high content of Pd2+ oxidation state, and resistance to deactivation by carbonates, bicarbonates, and water. The Pd/Al2O3-x catalyst shows increased stability with respect to a Pd/Al2O3 counterpart during simulated aging in alternating reducing and oxidizing conditions due to stronger interactions with the support. This study demonstrates that defect engineering of non-reducible supports can constrain the evolution of active centers, which holds promising potential for widespread utilization across diverse industrial catalytic processes, including various hydrogenation and oxidation reactions.

Enabling long-distance hydrogen spillover in nonreducible metal-organic frameworks for catalytic reaction

Hydrogen spillover is an extraordinary effect in heterogeneous catalysis and hydrogen storage, which refers to the surface migration of metal particle-activated hydrogen atoms over the solid supports. Historical studies on this phenomenon have mostly been limited to reducible metal oxides where the long-distance proton-electron coupled migration mechanism has been established, yet the key question remains on how to surmount short-distance and defect-dependent hydrogen migration on nonreducible supports. By demerging hydrogen migration and hydrogenation reaction, here we demonstrate that the hydrogen spillover in nonreducible metal-organic frameworks (MOFs) can be finely modulated by the ligand functional groups or embedded water molecules, enabling significant long-distance (exceed 50 nm) movement of activated hydrogen. Furthermore, using sandwich nanostructured MOFs@Pt@MOFs as catalysts, we achieve highly selective hydrogenation of N-heteroarenes via controllable hydrogen spillover from Pt to MOFs-shell. We anticipate that this work will enhance the understanding of hydrogen spillover and shed light on de novo design of MOFs supported catalysts for many important reactions involving hydrogen.

Exploring the Interfacial Hydrogen Transfer between Pt and the Siliceous Framework and Its Promotional Effect on the Isotope Catalytic Exchange.

Interfacial hydrogen transfer between metal particles and catalyst supports is a ubiquitous phenomenon in heterogeneous catalysis, and this occurrence on reducible supports has been established, yet controversies remain about how hydrogen transfer can take place on nonreducible supports, such as silica. Herein, highly dispersed Pt clusters supported on a series of porous silica materials with zeolitic or/and amorphous frameworks were prepared to interrogate the nature of hydrogen transfer and its promotional effect on H2-HDO isotope catalytic exchange. The formation of zeolitic frameworks upon these porous silica supports by hydrothermal crystallization greatly promotes the interfacial hydrogen bidirectional migration between metal clusters and supports. Benefiting from this transfer effect, the isotope exchange rate is enhanced by 10 times compared to that on the amorphous counterpart (e.g., Pt/SBA-15). In situ spectroscopic and theoretical studies suggest that the defective silanols formed within the zeolite framework serve as the reactive sites to bind HDO or H2O by hydrogen bonds. Under the electrostatic attraction interaction, the D of hydrogen-bonded HDO scrambles to the Pt site and the dissociated H on Pt simultaneously spills back to the electronegative oxygen atom of adsorbed water to attain H-D isotope exchange with an energy barrier of 0.43 eV. The reverse spillover D on Pt combines with the other H on Pt to form HD in the effluent. We anticipate that these findings are able to improve our understanding of hydrogen transfer between metal and silica supports and favor the catalyst design for the hydrogen-involving reaction.

Significantly enhanced catalytic performance of Pd nanocatalyst on AlOOH featuring abundant solid surface frustrated Lewis pair for improved hydrogen activation.

The catalytic performance of a catalyst is significantly influenced by its ability to activate hydrogen. Constructing frustrated Lewis pairs (FLPs) with the capacity for hydrogen dissociation on non-reducible supports remains a formidable challenge. Herein, we employed a straightforward method to synthesize a layered AlOOH featuring abundant OH defects suitable for constructing solid surface frustrated Lewis pair (ssFLP). The results indicated that the AlOOH-80 (synthesized at 80 °C) possessed an appropriate crystalline structure conducive to generating numerous OH defects, which facilitated the formation of ssFLP. This was further evidenced by the minimal water adsorption in the AlOOH-80, inversely correlated with the quantity of defects in the catalyst. As expected, the Pd loaded onto AlOOH (Pd/AlOOH-80) exhibited excellent catalytic activity in hydrogenation reactions, attributed to abundant defects available for constructing ssFLP. Remarkably, the Pd/AlOOH-80 catalyst, with larger-sized Pd nanoparticles, displayed notably superior activity compared to commercial Pd/Al2O3 and Pd/C, both featuring smaller-sized Pd nanoparticles. Evidently, under the influence of ssFLP, the size effect of Pd nanoparticles did not dominate, highlighting the pivotal role of ssFLP in enhancing catalytic performance. This catalyst also exhibited exceptionally high stability, indicating its potential for industrial 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.

Formation mechanisms of N2O and NH3 on Pd/ZrO2 and Pd/Al2O3 for NO reduction

Reducible and nonreducible supports usually display distinct properties on the size, valence, and coordination of Platinum group elements in supported metal oxide. However, there are few reports on the regulation of main and side reaction rates and inhibition of byproducts from the perspective of reaction kinetics. Here, we compare the N2O and NH3 formations of Pd supported on Al2O3 and ZrO2 in NO reductions. Pd/Al2O3 produces less N2O and NH3 in quantity than Pd/ZrO2, which could be due to the moderate metal-support interactions between Pd with higher average valence and Al2O3 with lower ability of electrons transfer. ZrO2 acted as an electron acceptor in NO reduction facilitating the formations of unstable nitrates and surface hydroxyls. In-situ DRIFTS and NAP-XPS results suggest that the N2O generation is directly related to nitrates with different stabilities: bridging, bidentate, and partial monodentate nitrates are active on Pd/ZrO2, whereas, only nitro and partial bridging nitrates are active on Pd/Al2O3. The NH3 is mainly originated from the reaction of nitrates to surface hydroxyls with different coordination numbers. This work clarifies the byproducts formation mechanism in NO reduction and opens up the research topics using in-situ spectroscopy methodology.

Improving the Efficiency of Hydrogen Spillover by an Organic Molecular Decoration Strategy for Enhanced Catalytic Hydrogenation Performance

Hydrogen migration from metal particles to the support, known as hydrogen spillover, has provided insights for designing highly efficient catalysts in catalytic processes involving hydrogen. A facile and controllable strategy is highly desired to achieve an effective hydrogen spillover effect on nonreducible oxides for catalytic performance optimization and clarifying the catalytic function of hydrogen spillover. Here, we provide an organic molecular decoration (OMD) strategy obtained by the molecular layer deposition-like pulse method for facilitating hydrogen spillover over the nonreducible silica support. After decorating with the fluoroalkylsilane (FAS) molecular layer, the hydrogen spillover effect over the catalysts (xFAS-Pt/SBA-15) is greatly enhanced due to the presence of carbonaceous species compared with the original Pt/SBA-15. The amount of hydrogen spillover can also be precisely regulated by controlling the FAS pulse number. For cinnamaldehyde hydrogenation, xFAS-Pt/SBA-15 presents superior catalytic performance versus its untreated counterpart and the sample decorated via the traditional method. Also, the catalytic activity varies based on the FAS pulse number, showing a linear correlation with the amount of hydrogen spillover. The altered adsorption behavior of the reactant plays an important role in the hydrogenation selectivity. This facile OMD strategy for efficient hydrogen spillover is general and may have potential applications in many heterogeneous reactions.

Metal-Support Interactions in Heterogeneous Catalysis: DFT Calculations on the Interaction of Copper Nanoparticles with Magnesium Oxide.

Oxide supports play an important role in enhancing the catalytic properties of transition metal nanoparticles in heterogeneous catalysis. How extensively interactions between the oxide support and the nanoparticles impact the electronic structure as well as the surface properties of the nanoparticles is hence of high interest. In this study, the influence of a magnesium oxide support on the properties of copper nanoparticles with different size, shape, and adsorption sites is investigated using density functional theory (DFT) calculations. By proposing simple models to reduce the cost of the calculations while maintaining the accuracy of the results, we show using the nonreducible oxide support MgO as an example that there is no significant influence of the MgO support on the electronic structure of the copper nanoparticles, with the exception of adsorption directly at the Cu-MgO interface. We also propose a simplified methodology that allows us to reduce the cost of the calculations, while the accuracy of the results is maintained. We demonstrate in addition that the Cu nanowire model corresponds well to the nanoparticle model, which reduces the computational cost even further.

Support Effect and Stability of Inverse Fe1(OH)x/Pt Single-Site Interfacial Structured Catalysts for Preferential CO Oxidation in H2

Preferential oxidation of CO in hydrogen (PROX) has been regarded as a promising method for removing a trace amount of CO to a parts-per-million (ppm) level to provide pure hydrogen fuel for polymer-electrolyte membrane fuel cells. Recently, we reported that SiO2-supported Pt nanoparticles with atomically dispersed Fe1(OH)x decoration exhibited exceptional CO removal in a very broad temperature window of −75–107 °C in the PROX reaction because of enriched interfaces and remarkably high reducibility of the iron species. Here, we further investigated the support effect on the catalytic performance of this inverse Fe1(OH)x/Pt single-site interfacial structure, as well as their stabilities under high-temperature redox atmospheres. We found that Fe1(OH)x/Pt on nonreducible supports such as SiO2 and Al2O3 is more favorable for efficient CO removal than those on reducible supports (e.g., Fe2O3 and TiO2) in the PROX reaction. The inferior performance of the latter case is attributed to the creation of additional active interfaces to initiate competing H2 oxidation. High-temperature redox pretreatments of the optimized SiO2-supported Fe1(OH)x/Pt catalyst up to 500 °C did not cause any noticeable changes of the temperature window of complete CO removal, indicating that the inverse Fe1(OH)x/Pt single-site interface structure has high thermal stability against sintering. Further increasing the H2 concentration did not change the temperature window either. The above results suggest that the inverse Fe1(OH)x/Pt catalyst is very robust with high potential for practical applications and other catalytic reactions.

Boosting chiral carboxylic acid hydrogenation by tuning metal-MO -support interaction in Pt-ReO /TiO2 catalysts

Engineering the surface microenvironment by tuning the binary interactions between a supported metal with a secondary metal oxide (MOx) or support has been a common method for improving the catalytic performance of supported metal catalysts. However, few studies have investigated the ternary interactions among the metal, MOx, and support. Here, we report for the first time the formation of metal-MOx-support interaction (MMSI) in reducible TiO2-supported PtReOx catalysts, affording 87% yield and 100% ee in the tandem hydrogenation of an aqueous chiral cyclohexane-1,2-dicarboxylic acid into the corresponding diol; the catalytic activity is eight times higher than that obtained with non-reducible support counterparts in the same reaction via traditional batch synthesis with multiple steps and unfriendly reagents. Detailed experimental and computational studies suggest that the TiO2 crystalline phase-dependent density of the oxygen vacancies induces different Pt-ReOx-TiO2 interactions, which dominate the electron transfer therein and tune the adsorption strength of the carbonyl moiety of the substrate/intermediate, thus promoting the hydrogenation activity and selectivity. In addition, the strong MMSI endows the optimal rutile TiO2 supported PtReOx catalyst with an outstanding lifetime of 400 h in a fixed-bed reactor under acidic aqueous conditions and ensures efficient applications in the selective hydrogenation of aliphatic dicarboxylic acids and functional carboxylic acids. This work provides a promising strategy for the development of efficient and stable supported catalysts for the selective hydrogenation of diverse C–O and C=O bonds.

Ultra-high-temperature strong metal-support interactions in carbon-supported catalysts

Strong metal-support interactions (SMSIs), one of the core concepts in the field of catalysis, have a substantial influence on catalytic performance, especially stability. Conventional view holds that only reducible metal-oxide supports could induce a SMSI encapsulation state upon high-temperature treatments. Herein, we demonstrate a high-temperature SMSI between platinum and sulfur-doped carbon (S-C) supports, featuring charge transfer, suppression of H 2 /CO adsorption, and support of encapsulation. We find that the strong chemical interaction between platinum and sulfur atoms greatly suppresses platinum sintering at moderate temperatures of 300°C–700°C, along with the subsequent formation of SMSI encapsulation structures at high temperatures of 900°C–1,100°C. The high-temperature SMSI endowed the Pt/S-C catalysts with outstanding sintering resistance up to 1,100°C and enhanced electrocatalytic oxygen-reduction reaction (ORR) durability in H 2 –air proton-exchange membrane fuel cells (PEMFCs). • Strong metal-support interactions (SMSIs) have a substantial influence in catalysis • Non-reducible carbon support could also induce SMSI encapsulation • High-temperature SMSI enhances fuel cell durability Yin et al. report that non-reducible carbon support can induce SMSI states featuring electron transfer, suppressed H 2 /CO adsorption, and carbon encapsulation. This is shown to promote electrocatalytic ORR activity and durability in H 2 –air fuel cells.

Optimizing Pt Electronic States through Formation of a Schottky Junction on Non-reducible Metal-Organic Frameworks for Enhanced Photocatalysis.

Charge transfer between metal sites and supports is crucial for catalysis. Redox-inert supports are usually unfavorable due to their less electronic interaction with metal sites, which, we demonstrate, is not always correct. Herein, three metal-organic frameworks (MOFs) are chosen to mimic inert or active supports for Pt nanoparticles (NPs) and the photocatalysis is studied. Results demonstrate the formation of a Schottky junction between Pt and the MOFs, leading to the electron-donation effect of the MOFs. Under light irradiation, both the MOF electron-donation effect and Pt interband excitation dominate the Pt electron density. Compared with the "active" UiO-66 and MIL-125 supports, Pt NPs on the "inert" ZIF-8 exhibit higher electron density due to the higher Schottky barrier, resulting in superior photocatalytic activity. This work optimizes metal catalysts with non-reducible supports, and promotes the understanding of the relationship between the metal-support interaction and photocatalysis.

Towards Highly Loaded and Finely Dispersed CuO Catalysts via ADP: Effect of the Alumina Support

To meet current economic demands enforcing the replacement of platinum-group metals, extensively used in three-way-catalytic converters (TWC), research is driven towards low-cost and widely available base metals. However, to cope with their lower activity, high metal loadings must be coupled with increased dispersion. Herein, a series of CuO/Al2O3 samples is produced and the effect of different alumina supports’ properties on CuO dispersion, speciation and eventually on the TWC performance is studied. The alumina samples are synthesized via different methods, including soft-templating routes and flame spray pyrolysis, and compared with a commercial one, while CuO used as the catalytic active phase is added through ammonia-driven deposition–precipitation. As found, the large surface area and low crystallinity of the aluminas produced by soft-templating routes favor strong metal–support interaction, generating highly dispersed and strongly bonded CuO species at low loading and copper-aluminate phases at high loading. Notably, the use of amorphous mesoporous alumina completely prevents the formation of crystalline CuO even at 15 wt% Cu. Such high metal loading and dispersion capacity without the application of elevated calcination temperatures is one of the best reported for nonreducible supports. Catalytic evaluation of this material reveals a pronounced enhancement of oxidation activity with metal loading increase.

CO oxidation on MgAl2O4 supported Irn: activation of lattice oxygen in the subnanometer regime and emergence of nuclearity-activity volcano

Ir subnanometer clusters activate surface oxygen on a traditionally non-reducible MgAl2O4 support which leads to a more active two-site mechanism during low-temperature CO oxidation.

Strong metal-support interactions induced by an ultrafast laser

Supported metal catalysts play a crucial role in the modern industry. Constructing strong metal-support interactions (SMSI) is an effective means of regulating the interfacial properties of noble metal-based supported catalysts. Here, we propose a new strategy of ultrafast laser-induced SMSI that can be constructed on a CeO2-supported Pt system by confining electric field in localized interface. The nanoconfined field essentially boosts the formation of surface defects and metastable CeOx migration. The SMSI is evidenced by covering Pt nanoparticles with the CeOx thin overlayer and suppression of CO adsorption. The overlayer is permeable to the reactant molecules. Owing to the SMSI, the resulting Pt/CeO2 catalyst exhibits enhanced activity and stability for CO oxidation. This strategy of constructing SMSI can be extended not only to other noble metal systems (such as Au/TiO2, Pd/TiO2, and Pt/TiO2) but also on non-reducible oxide supports (such as Pt/Al2O3, Au/MgO, and Pt/SiO2), providing a universal way to engineer and develop high-performance supported noble metal catalysts.

Retraction Note to: Revisiting the Evolution of IR Spectra of CO Adsorbed on Au Nanoparticles Supported on Non-reducible Supports

Retraction Note to: Revisiting the Evolution of IR Spectra of CO Adsorbed on Au Nanoparticles Supported on Non-reducible Supports

Divanadium substituted keggin [PV2W10O40] on non-reducible supports-Al2O3 and SiO2: synthesis, characterization, and catalytic properties for oxidative dehydrogenation of propane

Molecular metal oxide cluster, K5[α-1,2-PV2W10O40] (PV2W10), was found to have intrinsic catalytic activity for the oxidative dehydrogenation of propane with high selectivity (> 80%) to propylene at low propane conversion (0.3%). Synthesis of dispersed PV2W10 in non-reducible supports, γ-Al2O3 and SiO2, was done by incipient wetness impregnation. The supported catalysts were characterized by IR, Raman spectroscopy, nitrogen adsorption, x-ray powder diffraction (PXRD), elemental analysis, hydrogen temperature-programmed reduction (H2–TPR), and ammonia temperature-programmed desorption (NH3–TPD). Catalytic testing of the supported PV2W10 at equimolar cluster concentration revealed that when supported in γ-Al2O3 it is more active (sevenfold increase in propane conversion) but in SiO2 it is more selective to propylene (94%). The observed performance was due to both an increase in reducibility and higher concentration of strong acid sites for PV2W10 supported in γ-Al2O3 versus SiO2. Lastly, PV2W10 was shown to remain intact under reaction conditions indicating its thermal and oxidative stability.

HCN production from formaldehyde during the selective catalytic reduction of NOx with NH3 over V2O5/WO3-TiO2

Raw exhaust gases may contain notable levels of formaldehyde that can negatively impact the efficiency of after-treatment systems. In the selective catalytic reduction (SCR) of NOx over V2O5/WO3-TiO2, formaldehyde was found to react with NH3 to produce HCN at concentrations above the threshold limit value set by environmental/safety organizations. Due to this side reaction, NH3 is consumed parasitically and the NOx conversion decreases by up to 15 %, even after compensating for the fraction of lost NH3. Under similar conditions, the non-reducible TiO2 support also produced HCN moderately, thereby showing that redox sites promote the reaction but are not a necessary condition. To understand the chemistry responsible for HCN formation, the roles of reaction temperature, water, and oxygen were investigated. Our results suggest a new pathway for HCN production through the direct reaction of formaldehyde and NH3, which is active at high temperature and does not proceed through the formate route previously proposed.

Low-Temperature Propylene Epoxidation Activity of CuO–CeO2 Catalyst with CO + O2: Role of Metal–Support Interaction on the Reducibility and Catalytic Property of CuOx Species

Epoxidation of propylene into propylene oxide (PO) in the gas phase is a highly challenging reaction. Cu-based catalysts have been active for this reaction, but the state of Cu as an active species is still debatable. In this paper, we report the propylene epoxidation activity of solution combustion synthesized Cu/CeO2 catalysts with the CO + O2 mixture at low temperatures (50–100 °C) peaking at ∼80 °C. The highest PO yield was obtained with 20–25% Cu loading in CeO2. In contrast, the reaction over the catalyst containing nonreducible support such as Cu/SiO2 occurred above 170 °C. Detailed structural characterization indicated two types of Cu species such as Cu2+ partly (∼3%) dissolved in CeO2 forming a CuxCe1–xO2−δ phase and the remaining amount formed highly dispersed CuO as a separate phase. Thus, the highest activity relates to the optimum presence of CuO along with Ce1–xCuxO2−δ. The reducibility of the Cu species in two phases was significantly shifted toward lower temperatures, indicating strong electronic interaction between the two phases. The substituted Cu2+ was reduced first, and then, the bulk CuO reduction was initiated. In situ spectroscopic studies showed Cu+ formation from Cu2+ over Cu/CeO2 catalysts even at room temperature unlike in CeO2 or CuO + CeO2 physical mixtures, indicating strong electronic interaction between Ce1–xCuxO2−δ and CuO phases on CO adsorption in the Cu/CeO2 catalyst. It is proposed that substituted Cu2+ along with Ce4+ is reduced easily, and then, Ce3+ promotes the reduction of the interfacial CuO phase that might donate active oxygen species for epoxidation reaction.

CO2 Hydrogenation on Cu/Al2 O3 : Role of the Metal/Support Interface in Driving Activity and Selectivity of a Bifunctional Catalyst.

Selective hydrogenation of CO2 into methanol is a key sustainable technology, where Cu/Al2 O3 prepared by surface organometallic chemistry displays high activity towards CO2 hydrogenation compared to Cu/SiO2 , yielding CH3 OH, dimethyl ether (DME), and CO. CH3 OH formation rate increases due to the metal-oxide interface and involves formate intermediates according to advanced spectroscopy and DFT calculations. Al2 O3 promotes the subsequent conversion of CH3 OH to DME, showing bifunctional catalysis, but also increases the rate of CO formation. The latter takes place 1) directly by activation of CO2 at the metal-oxide interface, and 2) indirectly by the conversion of formate surface species and CH3 OH to methyl formate, which is further decomposed into CH3 OH and CO. This study shows how Al2 O3 , a Lewis acidic and non-reducible support, can promote CO2 hydrogenation by enabling multiple competitive reaction pathways on the oxide and metal-oxide interface.