Metal-support Interaction Effect Research Articles

Crystal Facet Controlled Metal-Support Interaction in Uricase Mimics for Highly Efficient Hyperuricemia Treatment.

The effect of strong metal-support interaction (SMSI) has never been systematically studied in the field of nanozyme-based catalysis before. Herein, by coupling two different Pd crystal facets with MnO2, i.e., (100) by Pd cube (Pdc) and (111) by Pd icosahedron (Pdi), we observed the reconstruction of Pd atomic structure within the Pd-MnO2 interface, with the reconstructed Pdc (100) facet more disordered than Pdi (111), verifying the existence of SMSI in such coupled system. The rearranged Pd atoms in the interface resulted in enhanced uricase-like catalytic activity, with Pdc@MnO2 demonstrating the best catalytic performance. Theoretical calculations suggested that a more disordered Pd interface led to stronger interactions with intermediates during the uricolytic process. In vitro cell experiments and in vivo therapy results demonstrated excellent biocompatibility, therapeutic effect, and biosafety for their potential hyperuricemia treatment. Our work provides a brand-new perspective for the design of highly efficient uricase-mimic catalysts.

Modulation effect of support on active metals in the Fe-Ni based catalysts: Insight into the electronic metal-support interaction (EMSI) effect in the CO-SCR reaction

Supported catalysts have been extensively investigated and implemented in the industry due to their cost-effectiveness and promising catalytic performance. However, due to the general inert nature of the support itself, its role in the catalyst performance is often neglected and therefore not well understood despite the consideration of the physical properties of the support. This study applies the concept of electronic metal-support interaction (EMSI) to explore the impact of various supports on the active metals in Fe-Ni-based catalysts for the CO-selective catalytic reduction reaction. Through density functional theory calculations and several advanced characterizations, it can be confirmed that the EMSI effect can modify the valence states of active metals and foster interaction between different active metals, thereby influencing the reactant adsorption and catalyst performance greatly. These findings highlight the significant impact of the support on the chemical states of active metals, having far-reaching implications for designing and optimizing the supported industrial catalysts.

Ni-Co alloy supported on CeO2 by SiO2 encapsulation for dry reforming of methane

Dry reforming of methane (DRM) is a highly endothermic reaction that needs harsh condition of high temperature for syngas production, which is challenged by developing catalysts with properties of anti-sintering and low carbon deposition. This work synthesized confined catalysts of (Co-Ni/CeO2)@SiO2 for DRM reaction. The catalysts possessed multifunction including size and alloy effects, metal-support interaction and confinement effect, which contributed to high rates of CH4 and CO2, marginal sintering of NiCo alloy and trace carbon deposition. The (3Ni-3Co/CeO2)@SiO2 catalyst reached rates as high as 4.74 mmol/(gNi·s) and 5.57 mmol/(gNi·s) for CH4 and CO2, respectively, at 1023 K. The rates were keeping stable for at least 36 h on stream. The characterizations of used samples revealed the limited size change of NiCo alloy and the low carbon deposition. The work provides valuable guidance for developing stable catalysts for DRM and other high temperature reactions.

CO2 Conversion via Low-Temperature RWGS Enabled by Multicomponent Catalysts: Could Transition Metals Outperform Pt?

AbstractIn the context of CO2 valorisation, the reverse water–gas shift reaction (RWGS) is gathering momentum since it represents a direct route for CO2 reduction to CO. The endothermic nature of the reaction posses a challenge when it comes to process energy demand making necessary the design of effective low-temperature RWGS catalysts. Herein, multicomponent Cs-promoted Cu, Ni and Pt catalysts supported on TiO2 have been studied in the low-temperature RWGS. Cs resulted an efficient promoter affecting the redox properties of the different catalysts and favouring a strong metal-support interaction effect thus modulating the catalytic behaviour of the different systems. Positive impact of Cs is shown over the different catalysts and overall, it greatly benefits CO selectivity. For instance, Cs incorporation over Ni/TiO2 catalysts increased CO selectivity from 0 to almost 50%. Pt-based catalysts present the best activity/selectivity balance although CuCs/TiO2 catalyst present comparable catalytic activity to Pt-studied systems reaching commendable activity and CO selectivity levels, being an economically appealing alternative for this process.

Experimental and theoretical unraveling of the electrocatalytic hydrodechlorination of chlorinated phenol using Pd promoted by oxygen vacancies in TiO2 array

The electrocatalytic dichlorination (EHDC) shows a promising potential to degrade chlorinated phenols (CPs). It is also a green technology in reducing the corresponding hazardous impact on the environment. In this study, we constructed a catalytic structure which was Pd on a TiO2 array with oxygen vacancies on carbon fibre paper substrate (Pd/TiO2/CFP) by a relatively mild route. Due to the presence of the oxygen vacancies, the resulting strong metal-support interaction (SMSI) effect has been identified which featured a redistribution of spatial charge in Pd/TiO2. The electron flow from the oxygen vacancies in the TiO2 to Pd facilitated the adsorption of Pd with 4-chlorophenol (4-CP) and endowed the Pd metal with an improved chemical reaction kinetics even at a low Pd loading. Experimentally, we studied the dependence of pH, concentration of 4-CP, and working potential on the reaction conditions of EHDC. The results showed that the conversion of 4-CP reached 100 % within 180 min with an apparent rate constant of 2.9 × 10-2 min−1 and the dominant product was phenol (P). The multi-cycle test illustrated that the Pd/TiO2/CFP electrode showed superior stability. The results also revealed that the comprehensive catalytic behavior was much better than those of the Pd/CFP and the TiO2/CFP electrodes. The density function theory (DFT) calculations indicated that 4-CP was more preferably absorbed on Pd/TiO2/CFP than Pd/CFP due to the SMSI assistance. This study provides a valuable guide in the preparation of precious metal-based electrodes for EHDC with a reduced loading and cost but without performance compromise.

Research progress of metal oxide supports for fuel cells electrocatalysts

AbstractFuel cell technology, as a new way of energy conversion, is widely used in various fields. At present, the electrocatalyst, as one of the key components of the electrochemical reaction of fuel cells, still suffers from the problems of high cost, low activity and poor stability. Excellent fuel cell electrocatalysts must have excellent catalytic activity, anti‐poisoning ability, electrical conductivity and stability. Metal oxides with corrosion resistance, electrochemical stability and strong metal support interaction effects have been intensively studied. The influence of the synthesis method on the catalytic performance is also crucial. In this review, the importance of fuel cells and their catalysts is introduced. The characteristics of catalysts with three metal oxides, titanium dioxide, cerium dioxide and tungsten oxide, as supports, preparation methods and applications in different fuel cells are reviewed. The synthesis of metal oxide supported catalysts by impregnation, precipitation and hydrothermal methods is described. Finally, the research on metal oxide supported catalysts is prospected.

Which is better for converting furfural into furfuryl alcohol: The strong metal-support interaction effect or the formation of alloy?

Furfural, one of biomass raw materials, can be seen as a clean alternative energy to fossil energy. Cu-based catalysts have been studied mostly due to the excellent selectivity to furfuryl alcohol. While keeping the stability of Cu-based catalysts under high temperature is still a challenge. Thus, a more active and stable Ni-based catalyst is researched. While the high yield of furfuryl alcohol was difficult to obtained over Ni catalysts. A catalyst (5 % Ni/Ce0.9Sn0.1O2) that combines stability and selectivity was prepared with enhanced activity which was different with the NiSn alloy. Combined with the characterizations of XRD, XPS, TEM, CO-TPD and H2-TPR, it has been proven that the enhanced strong interaction between Ni and Ce0.9Sn0.1O2 is much more effective in forming furfuryl alcohol than the effect of the Ni3Sn4 alloy.

TiO2 Nanolayer–Coated Carbon as Pt Support for Enhanced Methanol Oxidation Reaction

Abstract To facilitate the large-scale application of direct methanol fuel cells (DMFCs), the issue of low Pt/C durability due to Pt degradation and carbon corrosion in harsh DMFC operating conditions must be addressed. A promising strategy is to hybridize metal oxides with carbon materials, resulting in a durable and conductive support that exhibits a strong metal-support interaction (SMSI) effect on platinum nanoparticles (Pt NPs). In this study, we introduced a TiO2 coating on carbon black, creating a TiO2 nanolayer between Pt and carbon black. The nanolayer not only protects the carbon black but also activates the SMSI effect on Pt. The resulting Pt/C@TiO2 electrocatalyst exhibits superior durability than commercial Pt/C. After the accelerated durability test, the mass activity loss of the methanol oxidation reaction (MOR) of Pt/C@TiO2 (32%) is significantly lower than that of Pt/C (46.8%). Moreover, the MOR activity of Pt/C@TiO2 is higher than Pt/C as well. It suggests that Pt/C@TiO2 shows great potential as a highly durable and active electrocatalyst for DMFCs.

Regulating electronic metal-support interaction (EMSI) via pore-confinement to enhance non-thermal plasma catalytic oxidation of toluene

The non-thermal plasma catalysis holds great promise for VOCs removal, and the development of catalysts with electronic metal-support interaction (EMSI) effect is beneficial for VOCs removal. In this study, we prepared three Mn@M catalysts with EMSI coordination structures by encapsulating MnOx particles within the mesoporous molecular sieve (MCM-41) with different pore size (2.9 nm, 4.4 nm, and 7.9 nm), and investigated the effect of pore size on EMSI and non-thermal plasma catalytic performance of Mn@M for toluene. Among three catalysts, Mn@M2 with an average pore size of 4.38 nm exhibited the strongest EMSI and superior redox capabilities, thus demonstrating the highest mineralization rate, carbon balance, and CO2 selectivity for plasma catalytic oxidation of toluene. The EMSI effect leads to the formation of electron-rich and electron-poor centers on the Si-O-Mn-O bond, facilitating the generation of reactive oxygen species and enhancing the oxygen cycle. In addition, the reaction degradation pathway was investigated using in situ DRIFTS and GC–MS. This study provides valuable insights for designing highly effective supported catalysts by pore confinement to degrade VOCs in adsorption-plasma catalysis system.

Facile synthesis of surface oxygen vacancy and Ti3+ defects in SrTiO3 perovskite coupled g-C3N4 decorated with Au ternary nanocomposites for enhancing electrocatalytic activity from acidic and natural seawater conditions

The development of efficient electrocatalysts became vital to resolving the ongoing clean energy crises and environmental issues, wherein high-performance catalysts for the improved electrocatalytic hydrogen evolution reaction (EHER) are demanded. To meet this goal, an advanced and green ultrasonic-assisted pulsed laser ablation in liquid technique was used to prepare surface oxygen vacancy and Ti3+ defects in perovskite-based ternary nanocomposites (PTNCs) decorated with Au@SrTiO3/g-C3N4. An effective cathode was designed using Au@SrTiO3/g–C3N4–decorated PTNCs for EHER that operated in an acidic media of 0.5 M H2SO4. The optimized Au@SrTiO3/g-C3N4 PTNCs revealed an improved EHER at a very low over-potential of 0.082 V at a cathodic current density (J) of −10 mA/cm2, high double-layer capacitance (679.8 μF/cm2), large electrochemical surface area (19.4 cm2), high mass activity (198.35 A/g), high specific activity (2.91 mA/cm2), high surface charge density (0.0404 C/cm2), high catalytic active sites (4.19 × 10−7 mol/cm2), and exceptional long-term stability at 50 h, respectively. The Tafel slope of 45.36 mV/dec confirmed the presence of the Volmer-Heyrovsky mechanism to explain the enhanced EHER cycle of the prepared PTNCs. The improved electrocatalytic EHER performance was attributed to the induced synergistic strong metal-support interaction (SMSI) effect of the surface oxygen vacancy and Ti3+ defects in PTNCs that increased electrochemical surface area, high exposure of abundant active sites, improved intrinsic kinetics, and fast charge transport, respectively. Moreover, Au@SrTiO3/g–C3N4–decorated PTNCs exhibit excellent natural seawater electrolysis in terms of EHER at a low over-potential of 0.300 V at a J = −10 mA/cm2 and long-term stability at 10 h, respectively. It is demonstrated that the proposed novel surface oxygen vacancy and Ti3+ defects in Au@SrTiO3/g-C3N4 PTNCs are effective electrocatalysts can be beneficial for producing hydrogen from green technologies in future energy applications via interface engineering.

Strong metal support interaction (SMSI) and MoO3 synergistic effect of Pt-based catalysts on the promotion of CO activity and sulfur resistance.

In industrial applications, Pt-based catalysts for CO oxidation have the dual challenges of CO self-poisoning and SO2 toxicity. This study used synthetic Keggin-type H3PMo12O40 (PMA) as the site of Pt, and the Pt-MoO3 produced by decomposition of PMA was anchored to TiO2 to construct the dual-interface structure of Pt-MoO3 and Pt-TiO2, abbreviated as Pt-P&M/TiO2. Pt-0.125P&M/TiO2 with a molar ratio of Pt to PMA of 8:1 showed both good CO oxidation activity and SO2 tolerance. In the CO activity test, the CO complete conversion temperature T100 of Pt-0.125P&M/TiO2 was 113 ℃ (compared with 135 ℃ for Pt/TiO2). In the SO2 resistance test, the conversion efficiency of Pt-0.125P&M/TiO2 at 170 ℃ remained at 60% after 72h, while that of Pt/TiO2 was only 13%. H2-TPR and XPS tests revealed that lattice oxygen provided by TiO2 and hydroxyl produced by MoO3 increased the CO reaction rate on Pt. According to the DFT theoretical calculation, the electronegative MoO3 attracted the d-orbital electrons of Pt, which reduced the adsorption energy of CO and SO2 from - 4.15eV and - 2.54eV to - 3.56eV and - 1.52eV, respectively, and further weakened the influence of strong CO adsorption and SO2 poisoning on the catalyst. This work explored the relationship between catalyst structure and catalyst performance and provided a feasible technical idea for the design of high-performance CO catalysts in industrial applications.

MgO impregnation to Al2O3 supported Ni catalyst for SYNGAS production using greenhouse gases: Some aspects of chemical state of Ni species

Al2O3 was prepared by sol–gel method and stabilized at 700 °C, then impregnated with 5, 15, and 30 wt% MgO to obtain the mixed oxide and stabilized again at 700 °C. The catalytic Ni/Al2O3 and Ni/Al2O3–MgO materials were prepared by impregnation method. The catalytic properties were studied on the dry reforming of methane (DRM) reaction using greenhouse gases (CO2+ CH4) to SYNGAS (Carbon Oxide/Hydrogen: CO/H2) at 700 °C for 70 h. The catalysts characterization includes TPR-H2, X-RD, BET, SEM, TPD-CO2, TPO-MS and TEM techniques. The CH4 and CO2 conversion was more stable in the Ni-base catalysts supported on mixed Al2O3–MgO oxides than in the Ni/Al2O3 sample. The Ni/Al2O3–MgO(5%) catalyst showed a lower presence of C (carbon) as evidenced by TPO-MS, XRD, SEM and TEM characterization. This finding reveals that a low quantity of MgO in the catalyst, delays the carbon development and may be associated with the basic character and a greater dispersion of this oxide on the surface of the alumina. In addition to the Ni–Mg–Al–O spinel formation, which enhanced the strong metal-support interaction (SMSI) effect between the support and the active phase. The Ni sintering of the catalysts after catalytic reaction is likely at the expenses of Ni–Al–O and MgNiO2 phases as was evidenced by XRD technique. The effect of the oxidation state of the active phase on the Ni/Al2O3–MgO (5%) sample had influence on the CO2 transformation, H2/CO ratio, basic sites, and stability in the C species.

Revealing the effect of metal-support interactions at the Ni/In2O3(111) interface on the selective CO2 hydrogenation

In2O3-supported Ni catalysts exhibit remarkable catalytic activity and selectivity in CO2 hydrogenation to methanol, but the underlying mechanisms and metal-oxide interactions during the reaction remain elusive. Herein, we investigate the Ni-In2O3 interaction by physical vapor deposition of Ni onto well-defined In2O3(111) thin films. In-situ near ambient-pressure X-ray photoelectron spectroscopy (NAP-XPS) was employed to probe the CO2 hydrogenation processes on these Ni/In2O3(111) model systems. Our results reveal that the small Ni clusters supported on the In2O3(111) surface at low Ni coverages exhibit cationic states. The chemical bonding and associated electron transfer at the Ni/In2O3(111) interface play crucial roles in the activation of H2 and CO2. Importantly, reaction intermediates (CO3*, OH, and HCOO*) are readily formed and desorbed under CO2 hydrogenation conditions. Our study highlights the significance of metal-support interactions on the selectivity of CO2 hydrogenation. These findings provide valuable insights into the rational design of advanced In2O3-based catalysts for CO2 hydrogenation.

Silver-induced adsorption optimization of adjacent Co tetrahedral sites for enhanced oxygen reduction/evolution reaction

Physical structure change of catalysts based on the electronic metal-support interaction (EMSI) effects is a prospective strategy to regulate the surface electronic structure of catalysts and further enhance their catalytic performance. To optimize the constrained intrinsic oxygen evolution reaction/oxygen reduction reaction (OER/ORR) activity of spinel MnCo2O4, we present a facile hydrothermal and photoreduction strategy to synthesize the Ag and MnCo2O4 supported on N-doped carbon nanotubes (Ag-MnCoO/NCNTs) with the EMSI effect. Ag-MnCoO/NCNTs as catalyst shows enhanced performance for OER (overpotential of 340 mV) and ORR (half-wave potential of 0.80 V). Furthermore, a zinc-air battery is assembled based on Ag-MnCoO/NCNTs cathode, which affords an open circuit potential of 1.49 V and favorable cycling performance for 200 h. Theoretical calculations illustrate the introduction of Ag reduces the charge density of the tetrahedral Co site along the direction of the dangling bonds and optimizes the adsorption of oxygen intermediates on tetrahedral Co, thus lowering the reaction activation energy and improving its oxygen catalytic activity. This work provides new insights to guide the fabrication of advanced oxygen electrocatalysts.

Anti-sintering Ni-ZnO catalyst stabilized by a dual protection of SMSI and carbon for efficient RWGS reaction

Colloidal nanoparticles with uniform particle size distribution, tailored exposed facets, and controllable compositions appealed to broad interests in heterogeneous catalysis. Nevertheless, due to the strong attachment of capping agents to the nanoparticles, cleaning the nanoparticle surface without changing the size of nanoparticles remains a significant challenge. Herein, based on the double confinement of the strong metal-support interaction (SMSI) effect and carbon encapsulation, the well-stabilized Ni-ZnO-S3 catalyst was successfully synthesized. The size of Ni nanoparticles after calcination in the sequence of H2-N2 mixture, air, and H2-N2 mixture remained below 5 nm. Due to no significant size change in Ni nanoparticles, the prepared Ni-ZnO-S3 catalyst served well as model catalysts in the RWGS reaction, where the CO2 conversion and CO yield increased proportionally to the Ni loading weight. According to the result of in-situ FTIR, an associative mechanism of RWGS reaction over Ni-ZnO-S3 was also identified. Therefore, this dual protect strategy provides a potential solution for building highly anti-sintering catalysts based on the colloidal synthesis route.

Cobalt Stabilization through Mesopore Confinement on TiO2 Support for Fischer-Tropsch Reaction.

Cobalt supported on mesostructured TiO2 catalysts has been prepared by a wet-impregnation method. The Co/TiO2 catalytic system showed better catalytic performance after support calcination at 380 °C. Co nanoparticles appeared well distributed along the mesopore channels of TiO2. After reduction pretreatment and reaction, a drastic structural change leads to mesopore structure collapse and the dispersion of the Co nanoparticles on the external surface. Along this complex process, Co species first form discrete nanoparticles inside the pore and then diffuse out as the pore collapses. Through this confinement, a strong metal-support interaction effect is hindered, and highly stable metal active sites lead to better performance for Fischer-Tropsch synthesis reaction toward C5+ products.

Systematic Characterization of Electronic Metal-Support Interactions in Ceria-Supported Pt Particles.

Electronic metal-support interactions affect the chemical and catalytic properties of metal particles supported on reducible metal oxides, but their characterization is challenging due to the complexity of the electronic structure of these systems. These interactions often involve different states with varying numbers and positions of strongly correlated d or f electrons and the corresponding polarons. In this work, we present an approach to characterize electronic metal-support interactions by means of computationally efficient density functional calculations within the projector augmented wave method. We describe Ce3+ cations with potentials that include a Ce4f electron in the frozen core, overcoming prevalent convergence and 4f electron localization issues. We systematically explore the stability and chemical properties of different electronic states for a Pt8/CeO2(111) model system, revealing the predominant effect of electronic metal-support interactions on Pt atoms located directly at the metal-oxide interface. Adsorption energies and the reactivity of these interface Pt atoms vary significantly upon donation of electrons to the oxide support, pointing to a strategy to selectively activate interfacial sites of metal particles supported on reducible metal oxides.

Chemical Kinetics of Metal Single Atom and Nanocluster Formation on Surfaces: An Example of Pt on Hexagonal Boron Nitride.

The production of atomically dispersed metal catalysts remains a significant challenge in the field of heterogeneous catalysis due to coexistence with continuously packed sites such as nanoclusters and nanoparticles. This work presents a comprehensive guidance on how to increase the degree of atomization through a selection of appropriate experimental conditions and supports. It is based on a rigorous macro-kinetic theory that captures relevant competing processes of nucleation and formation of single atoms stabilized by point defects. The effects of metal-support interactions and deposition parameters on the resulting single atom to nanocluster ratio as well as the role of metal centers formed on point defects in the kinetics of nucleation have been established, thus paving the way to guided synthesis of single atom catalysts. The predictions are supported by experimental results on sputter deposition of Pt on exfoliated hexagonal boron nitride, as imaged by aberration-corrected scanning transmission electron microscopy.

Controlling the metal-support interaction of Cu/ZnO sorbent to improve its ultra-deep desulfurization performance for thiophene in coke oven gas

The deep removal of thiophene sulfur from coke oven gas (COG) is an important aspect for the subsequent production of COG to natural gas via methanation. In this process, copper-based sorbents exhibit excellent desulfurization activity. However, the activity of the sorbent depends largely on the interaction between Cu and Zn in the sorbent, which is often used to stabilize metal particles and regulate the activity and stability of the sorbent. Despite a large number of studies on metal-support interaction, there is still a lack of understanding of the effects of metal-support interaction of different strengths on the structure and performance of sorbents. In this work, Cu/ZnO sorbents with different strengths of metal-support interaction were successfully synthesized to elucidate the effect of the interaction between Cu and Zn on the performance of thiophene removal. The reconstruction process of the sorbent (different component ratios) changed the CuZn interaction. For weakly interacting sorbents, the reconstruction process enhanced the interaction between the two components, which is conducive to electron transfer and overall activity improvement. On the contrary, for sorbents with strong interaction, the reconstruction process was hindered.

Enhanced radical scavenging performance of Pt@CeO2 via strong metal-support interaction effect for improving durability of proton exchange membrane fuel cell

Since scavenging free radical is regarded as an efficient strategy to enhance the durability of proton exchange membrane fuel cells (PEMFCs), strong metal-support interaction (SMSI) effect between metal and reducible oxide supports is employed as a strategy to moderate the number of accessible active sites for reduction-oxidation reaction. Enriched Pt–CeO2 interface to enhance SMSI effect is achieved as well via constructing multicore-shell structure Pt@CeO2. Theoretical calculation confirms that SMSI effect at Pt–CeO2 interface endows electrons flowing from Pt to CeO2 to reduce the formation energy of oxygen vacancies, while Pt@CeO2 with higher magnitude of lattice distortion plan provides enriched Pt–CeO2 interface that made more concentration of Ce3+ ions feasible. Results show that better free radical scavenging performance is achieved with higher concentration of Ce3+ ions in Pt@CeO2. Based on the open circuit voltage (OCV) test, the Pt@CeO2-modified membrane in this work decays at only 70% of the commercial membrane, while 65% of the maximum power is still maintained after the test. This superior performance to the commercial membrane indicates this designed structure with SMSI effect could be considered as a potential route to solve the free radical problem in PEM for enhanced durability of PEMFCs.