Strong Metal-support Interaction Research Articles

Tuning the strong metal support interaction of the Fischer-Tropsch synthesis silica-coated cobalt-based nano-catalyst

The catalyst is crucial in enhancing productivity within the Fischer-Tropsch synthesis (FTS). The metal support interaction (MSI) plays a pivotal role in the FTS catalyst performance, impacting activity, stability, and selectivity. he configuration and composition of the catalyst dramatically impact MSI, with a strong MSI (SMSI) specified for the core-shell structure. In this study, two methods consisting of chemical treatment of etching and adding a promoter (Ru) for tuning the SMSI of the FTS catalyst are presented, and their footprints on the catalysts’ performance are screened by utilizing various characterization tests, molecular dynamic simulation, and catalytic tests. It is recognized that the silica interfacial perimeter acts as a barrier that restricts the charge transfer and boosts the SMSI in the silica-coated catalyst. Conversely, the etched catalyst exhibits a moderate MSI, contributing to increased reducibility, stability, and activity. Furthermore, the Ru-doped etched catalyst represents the optimum MSI, resulting in the highest overall performance.

Core–shell CoN@Co ultra-stable nanoparticles on biochar for contamination remediation in water and soil

Nanomaterials have been extensively employed in various applications over the past several decades, however, the stability of functional nanoparticle catalysts (NPCs) for effective degradation of organic contaminants remains a significant challenge. Herein, we present a cost-effective biochar loaded uniformly dispersed ultra-stable Co nanoparticles with an average diameter of 8 nm as a highly efficient peroxymonosulfate (PMS) activation catalyst. The reactive radicals produced from the catalyst/PMS system are able to degrade several model organic pollutants of environmental and public health concerns, including trichlorobiphenyl, bisphenol A and diethyl phthalate, with less pH limitation and Co2+ leaching. Mechanism investigation demonstrates that the CoN plays the key role in the catalyst stability and PMS activation via acid resistance and electron bridging effects, respectively. Meanwhile, the incorporation of nitrogen (N) and sulfur (S) atoms within the substrate is considered to bolster the adhesion strength between metal nanoparticles and the carbon matrix via strong metal-support interaction. The catalyst was further applied in practical treatment of water and soil polluted by organic pollutants, exhibiting a satisfactory degradation efficiency (> 90% in 60 min) for environmental applications.

Oxygen vacancy engineering in MOF-derived AuCu/ZnO bimetallic catalysts for methanol synthesis via CO2 hydrogenation

Three AuCu/ZnO bimetallic catalysts, AuCu/ZnO-BTC, AuCu/ZnO-BDC and AuCu/ZnO-MOF-74, were derived from various MOF precursors using facile hydrothermal methods. Among the resultant catalysts, the AuCu/ZnO-BTC catalyst possessed the best methanol synthesis activity, whose space time yield of methanol (STYMeOH) reached 359.0 gMeOH kgcat−1 h−1 at 250 °C under 3 MPa. Structural characterization reveals that in comparison with the AuCu/ZnO-BDC and AuCu/ZnO-MOF-74 catalysts, the AuCu/ZnO-BTC catalyst possessed higher specific surface area (SBET), tinier metal particle size, more oxygen vacancies, stronger metal-support interactions and larger amount of medium basic sites. In situ DRIFTS result demonstrates that formate (*HCOO) species were readily generated and bridged-methoxy (*b-OCH3) species were selectively formed on the AuCu/ZnO-BTC catalyst, which may be related with its abundant oxygen vacancies and responsible for its superior methanol synthesis activity. The present work derives high-performance AuCu/ZnO bimetallic catalysts from MOF precursors and provides new insight into structure-activity relationships for CO2 hydrogenation to methanol.

Optimizing Low-Temperature CO2 methanation with Aluminum-Doped Ni/CeO2 Catalysts: Insights into reaction pathway adjustments and strong Metal-Support interactions

Revealing the logical relationship between the structure, reaction mechanism and performance of the catalyst is a key step in the design of low-temperature CO2 methanation catalyst. The elemental Al was introduced into Ni/CeO2 using a co-precipitation method to form a composite support CeO2-Al2O3 loaded nickel-based catalyst. It was found that the incorporation of Al significantly improved the catalytic performance of low-temperature CO2 methanation. Notably, at a molar ratio of Al/Ce equal to 0.1, the catalyst exhibited optimal CO2 conversion of 88.83% and CH4 selectivity of 99.96% at 240 ℃. The addition of appropriate amounts of Al not only increases the specific surface area of the catalyst but also maintains a moderate strong interaction between metal Ni-support, thereby promoting the formation of active metal Ni species. Furthermore, the presence of Al leads to an increase in oxygen vacancy concentration, which facilitates the generation of numerous hydroxyl groups. Consequently, this alters the distribution of basic sites on the catalyst surface, resulting in a shift from the CO* pathway to a dual pathway involving both CO* and formate pathways. Remarkably, these divergent reaction pathways correspond to distinct active sites, thereby maximizing the utilization of each region within the catalyst. The diversity of reaction pathways and active sites represents pivotal factors for enhancing the catalytic performance of low-temperature CO2 methanation catalysts.

Tuning the Structure of Pd@Ni-Co Nanowires and Their Electrochemical Properties.

One-dimensional transition metal materials are promising supports for precious metals used in energy production processes. Due to their electrochemical properties, 3d-group metals (such as Ni, Co, and Fe) can actively interact with catalysts by a strong metal-support interaction. This study shows that changing the Ni:Co ratio makes it possible to modulate the structure of the catalyst supports, which, in turn, provides a tool for designing their electrical and electrochemical properties. For example, Ni1-Co9 shows the highest electrical conductivity (5.8-10-4 S/cm) among all of the materials examined. On the contrary, the Pd@Ni7-Co3 system presents the highest mass activity (>2000 mA mg-1) at 0.7 V, exceeding by several times that of commercial Pt/C (>300 mA mg-1) at the same potential. Our study opens the gateway for applications of bimetallic transition metal nanowires in catalytic conversion and energy production processes.

Engineering the Metal‐Support Interaction and Oxygen Vacancies on Ru@P‐Fe/Fe3O4 Nanorods for Synergetic Enhanced Electrocatalytic Nitrate‐to‐Ammonia Conversion

AbstractRuthenium (Ru) loaded catalysts show high activity and selectivity for ammonia (NH3) synthesis via electrochemical reduction of nitrate (NO3−), but their practical application is still restricted by their high cost and insufficient stability. Herein, a multi‐component electrocatalyst of Ru nanoclusters loaded on phosphorus‐doped/phosphate‐modified and oxygen vacancy (OV)‐rich Fe/Fe3O4 composite nanorods (Ru@P‐Fe/Fe3O4) to synergistically promote electrocatalytic NO3− reduction reaction (NO3−RR)‐to‐NH3 performance via strong metal‐support interaction (SMSI) is reported. Impressively, the best Ru@P‐Fe/Fe3O4 catalyst exhibits outstanding NO3−RR activity, selectivity, and durability in 0.1 M KNO3 + 0.5 M KOH solution, with an NH3 yield rate of 14.37 ± 0.21 mgNH3 h−1 cm−2 (1710.71 ± 25 mgNH3 h−1 mgRu−1) at −0.75 V versus reversible hydrogen electrode (vs. RHE), an NH3 Faradaic efficiency (FE) of 97.2% at −0.55 V vs. RHE, and a superior stability over 50 h, suppressing most of reported Fe‐based and Ru‐based electrocatalysts. The characterizations and theoretical calculations unveil that the SMSI between Ru nanoclusters and P‐Fe/Fe3O4 composite nanorods can promote the generation of OV, tune the electronic structure of Ru species, and stabilize Ru nanoclusters, thereby reducing the reaction energy barrier of NO3−RR‐to‐NH3, inhibiting the competitive hydrogen evolution reaction, and boosting the NH3 yield rate NH3 FE, and stability.

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.

Partial Exsolution Enables Superior Bifunctionality of Ir@SrIrO3 for Acidic Overall Water Splitting.

The pursuit of efficient and durable bifunctional electrocatalysts for overall water splitting in acidic media is highly desirable, albeit challenging. SrIrO3 based perovskites are electrochemically active for oxygen evolution reaction (OER), however, their inert activities toward hydrogen evolution reaction (HER) severely restrict the practical implementation in overall water splitting. Herein, an Ir@SrIrO3 heterojunction is newly developed by a partial exsolution approach, ensuring strong metal-support interaction for OER and HER. Notably, the Ir@SrIrO3-175 electrocatalyst, prepared by annealing SrIrO3 in 5% H2 atmosphere at 175 °C, delivers ultralow overpotentials of 229 mV at 10 mAcm-2 for OER and 28 mV at 10 mAcm-2 for HER, surpassing most recently reported bifunctional electrocatalysts. Moreover, the water electrolyzer using the Ir@SrIrO3-175 bifunctional electrocatalyst demonstrates the potential application prospect with high electrochemical performance and excellent durability in acidic environment. Theoretical calculations unveil that constructing Ir@SrIrO3 heterojunction regulates interfacial electronic redistribution, ultimately enabling low energy barriers for both OER and HER.

Preparation of nickel aluminate supported Ni nanocatalyst and its catalytic activity for ammonia decomposition to produce hydrogen

In this work, nickel aluminate (NiAl2O4) was synthesized through the co-precipitation, and then the Ni/NiAl2O4 catalysts were prepared by impregnation and the catalytic activity of the catalyst was evaluated. The results indicated that the synthesized NiAl2O4 had a large specific surface area, promoting the dispersion of Ni species and thus exposing more active sites. The strong metal-support interaction between Ni species and NiAl2O4 contributed significantly to the catalysts' high catalytic activity. Meanwhile, the strong basicity of catalyst could adjust the bond energy of Ni–N, which were conducive to desorption of the recombinant N2 from the metal surface. The Ni/NiAl2O4 catalyst with Ni loading of 50 wt% and calcination temperature of 700 oC exhibited the best catalytic activity with ammonia conversion of 95.3% at 550 oC under 30000 mL∙gcat-1∙h-1. This study offers a potential approach to developing a cost-effective and highly efficient catalyst for decomposing ammonia.

Amorphous metal-organic frameworks loaded on BiVO4 photoanodes with unique internal metal-like structure for promoting photoelectrochemical water splitting

Although ferrocene (Fc) based Metal-Organic Frameworks (MOFs) can act as oxygen evolution co-catalysts (OECs) for improvement of catalytic reactivity, the poor conductivity and lack of highly active metal sites limit its further application in photoelectrochemical (PEC) water splitting. Herein, the amorphous NiFc-MOF was grafted on BiVO4 photoanode (BiVO4@aNiFc-MOFs) for efficient PEC water splitting. This novel BiVO4@aNiFc-MOFs exhibits high current density of 4.34 mA cm−2 at 1.23 VRHE and relative low onset potential of 0.223 VRHE. The subsequent characterizations demonstrate that Ni species with metal-like state in bulk of aNiFc-MOFs form strong metal-support interaction with BiVO4, thereby promoting the interfacial charge transfer. Moreover, the surface of aNiFc-MOFs is short-range ordered with abundant coordinatively unsaturated Ni sites, creating a more favorable pathway for oxygen evolution reaction from thermodynamics. This work provides a simple method to design photoanodes with efficient OECs of amorphous MOFs for feasible PEC water splitting application.

X-ray standing wave characterization of the strong metal-support interaction in Co/TiOx model catalysts.

The strong metal-support interaction (SMSI) is a phenomenon observed in supported metal catalyst systems in which reducible metal oxide supports can form overlayers over the surface of active metal nanoparticles (NPs) under a hydrogen (H2) environment at elevated temperatures. SMSI has been shown to affect catalyst performance in many reactions by changing the type and number of active sites on the catalyst surface. Laboratory methods for the analysis of SMSI at the nanoparticle-ensemble level are lacking and mostly based on indirect evidence, such as gas chemisorption. Here, we demonstrate the possibility to detect and characterize SMSIs in Co/TiOx model catalysts using the laboratory X-ray standing wave (XSW) technique for a large ensemble of NPs at the bulk scale. We designed a thermally stable MoNx/SiNx periodic multilayer to retain XSW generation after reduction with H2 gas at 600°C. The model catalyst system was synthesized here by deposition of a thin TiOx layer on top of the periodic multilayer, followed by Co NP deposition via spare ablation. A partial encapsulation of Co NPs by TiOx was identified by analyzing the change in Ti atomic distribution. This novel methodological approach can be extended to observe surface restructuring of model catalysts in situ at high temperature (up to 1000°C) and pressure (≤3 mbar), and can also be relevant for fundamental studies in the thermal stability of membranes, as well as metallurgy.

Tuning Strong Metal–Support Interactions via Synergistic Alloying

Tuning Strong Metal–Support Interactions via Synergistic Alloying

Boosting the selective hydrogenation of biphenyl to cyclohexylbenzene over bimetallic Ni-Ru/SiO2 catalyst via enhancing strong metal-support interaction

Tuning the metal-support interaction (MSI) between highly dispersed nanosized metal particles and the support plays a pivotal role in the activity and selectivity of polyaromatics selective hydrogenation. In this work, the supported bimetallic Ni-Ru/SiO2-SEA catalyst was prepared by a strong electrostatic adsorption (SEA) strategy, and applied for the selective hydrogenation of biphenyl (BP) to cyclohexylbenzene (CHB). Compared to the catalysts prepared by the conventional incipient wetness impregnation method and Ni/SiO2-SEA, the significant effects of MSI and hydrogen spillover on Ni-Ru/SiO2-SEA facilitated the highly exposed and uniformly dispersed electron-deficient Niδ+ (0 < δ < 2) species, which could enhance adsorption and activation of the electron-withdrawing phenyl group and H2, thereby promoting the efficient and selective conversion of BP to CHB. At the conditions of 160 ℃ and 2 MPa H2 pressure, BP conversion over Ni-Ru/SiO2-SEA reached nearly 100 % within 3 h, achieving a remarkable selectivity of 97.9 % towards CHB, along with a high turnover frequency of 2756.9 h−1 for the active metallic Ni sites. Importantly, according to the kinetic simulations, the hydrogenation rate constant of Ni-Ru/SiO2-SEA was the highest (2.76 × 10-2 mol·g−1·h−1) among the employed catalysts. Moreover, after six consecutive cycles, no obvious decline in hydrogenation efficiency was observed, confirming the remarkable activity and stability of Ni-Ru/SiO2-SEA. Furthermore, the activation of BP and desorption of CHB pathway on the Niδ+ species were elaborated through temperature-programmed desorption characterization, highlighting the prominent contribution of MSI in enhancing the selective hydrogenation of polyaromatics.

Influence mechanism of Pd, Pt, Rh/γ-Al2O3 on NH3 formation for NO reduction by CO

The byproducts of NO reduction by CO have attracted great interest in the three-way catalysts, but the influence of active components (Pd, Pt, and Rh) on the formation mechanism is still elusive. Herein, Pd/, Pt/, and Rh/Al2O3 were prepared for investigating the NH3 formation during NO reduction by CO under wet conditions. The strongest metal-support interaction in Rh/Al2O3 is attributed to the highest interfacial Rh–O–Al bond from the results of XAFS and NMR. The smallest particle size and highest redox property on Rh/Al2O3 led to the highest NH3 yield below 300 °C. Pt/Al2O3 produced more NH3 than Pd/Al2O3 above 350 °C because of robust response to lattice oxygen reacted with NO and reduction by CO. The optimal strategy for minimizing byproducts on the premise of preserving three-way catalyst performance was the PtRh/γ-Al2O3 where the molar ratio of Pt: Rh was 9:1.

Unique role of silica in MOF-Derived High-Loading Palladium-on-Ceria single atom catalysts with excellent efficiency and durability

In most cases, the sintering tendency of supported metal single atoms could be attributed to the unstable structural characteristics of supports in demanding operating conditions, particularly for high-loading single-atom catalysts (SACs), ultimately resulting in deactivation. To address this issue, SiO2 is employed to enhance the structural stability of both supports and the supported Pd single atoms. SiO2 serves not only to prevent the collapse of support structures but also to promote the activation of surface oxygen species by facilitating electron transfer with the supports. This, in turn, establishes strong metal-support interactions (MSIs) to stabilize and activate atomically dispersed Pd species. Additionally, the electrons donated from Ce-O and Si-O to Pd atoms further catalyze the formation of oxygen vacancies, ultimately leading to significantly improved activity and durability in CO oxidation. Without SiO2, the instability of support structure, coupled with the weak MSIs, promotes the aggregation of Pd atoms, resulting in relatively lower catalytic activity and durability.

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.

Transition Metal Carbides as Supports for Catalytic Metal Particles: Recent Progress and Opportunities.

Transition metal carbides (TMCs) constitute excellent alternatives to traditional oxide-based supports for small metal particles, leading to strong metal-support interactions, which drastically modify the catalytic properties of the supported metal atoms. Moreover, they possess extremely high melting points and good resistance to carbon deposition and sulfur poisoning, and the catalytic activities of some TMCs per se have been shown to be similar to those of Pt-group metals for a considerable number of reactions. Therefore, the use of TMCs as supports can give rise to bifunctional catalysts with multiple active sites. However, at present, only TiC and MoxC have been tested experimentally as supports for metal particles, and it is largely unclear which combinations may best catalyze which chemical reactions. In this Perspective, we review the most significant works on the use of TMCs as supports for catalytic applications, assess the current status of the field, and identify key advances being made and challenges, with an eye to the future.

Oxygen-Vacancy-Induced Formation of Pt-Based Intermetallics on MXene with Strong Metal-Support Interactions for Efficient Oxygen Reduction Reaction.

The Pt-based alloys can moderate the binding energies of oxygenated species on the catalytic surface, endowing the superior catalytic performance towards oxygen reduction reaction (ORR). Nevertheless, it is still challenging to explore general methods to synthesize structurally ordered intermetallics with uniform distributions. Herein, the strong metal-support interaction is employed to facilitate the interdiffusion of Pt/M atoms by establishing a tunnel of oxygen vacancy on ultrathin Ti3C2Tx (MXene) sheets, synthesizing the ordered PtFe, PtCo, PtZn, PdFe, PdZn intermetallics loaded onto Ti3C2Tx. Furthermore, the in-situ generation of Ti-O from Ti3C2Tx could be bonded with Pt and forming Pt-O-Ti, resulting in charge redistribution through Pt-O-Ti structure. Theoretical calculations demonstrate that the valuable charge redistribution can be observed at the interface and extended even to at the distance of two nanometers from the interface, which can modulate the Pt-Pt distance, optimize Pt-O binding energy and enhance intrinsic activity towards ORR. The strong coupling interaction between PtFe and Ti3C2Tx containing the titanium oxide layer endows the high stability of the composites. This work not only presents a general synthesis strategy for intermetallics but also provides a new insight that metal-support interaction is essential for the structural evolution of intermetallics on materials with oxygen vacancies.

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.

Insights into Co and Fe-doping effects of mesoporous CeO2 catalysts for dry reforming of glycerol to syngas production

The dry reforming of glycerol (GDR) is one of the alternatives for syngas production by utilizing biodiesel byproduct glycerol and CO2. The development of highly active and stable catalyst is significantly important to achieve GDR process, and the current work provides insights into Co and Fe-doping effects of mesoporous CeO2 (CoFeCe) catalysts synthesized by the colloidal solution combustion method. The prepared catalysts presented the uniform mesoporous structure, the doping of Co and Fe metals resulted in stronger metal-support interaction. The GDR experimental data were compared with the non-stoichiometric thermodynamic equilibrium values. The conversions of glycerol and CO2 were increased with increasing the reaction temperatures due to the endothermic GDR reaction, and the H2/CO produced in syngas was in the range of 0.7–1.4. Due to the improvement of Co and Fe metals in the mesoporous structure of CeO2 catalyst, the 7CoFeCe catalyst exhibited excellent and stable GDR performance and no significant signs of deactivation were observed during 76 h test, and the results indicated that the enhanced interaction and high dispersion of Co and Fe in mesoporous CeO2 catalyst could inhibit carbon formation and promote GDR reaction.