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Here, homogeneous and heterogeneous catalysts have advantages and disadvantages. Molecular catalysts supported on heterogeneous materials have the potential to combine the advantages of both fields. Jabbour et al. report a detailed study of the 3D structure of an Ir-catalyst on silica.
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In sustainable chemical engineering, catalytic upgrading of lignocellulosic biomass has recently gained attention for producing renewable platform chemicals. To achieve maximal biomass utilization, upgrading the underutilized lignin components is essential. Among various catalysts for lignin upgrading, supported vanadia (V2O5) catalysts are promising because of their cost-effectiveness and tunability of either dopant metals or catalyst supports. Here, computational studies are conducted to derive rational design guidelines of supported V2O5 catalysts for accomplishing the high catalytic activity of lignin upgrading to phenol, a key compound for producing bioplastics and biofuel blendstocks. Guaiacol was used as the model compound since it comprises the highest portion of depolymerized lignin. Computational mechanistic studies for the catalytic guaiacol conversion to phenol were performed for the V2O5 catalysts on Titania (TiO2) and silica (SiO2) to explain higher experimental phenol yields on V2O5/SiO2 than V2O5/TiO2. The hydrogen migration from the methoxy group to the aryl ring was identified as a rate-determining step, and the overall activation energies on the two catalysts were compared. A structural analysis was carried out for the catalysts and rate-determining transition states to gain further insights from mechanistic studies. It was concluded that the tilt angle of the aryl group in the hydrogen migration transition state is a key descriptor determining the catalytic activity of phenol formation. These features correlate well with activation energies and experimental phenol yields, indicating that they provide design guidelines for supported metal catalysts for lignin upgrading before experiments.
Propylene is an important chemical feedstock that is largely produced via cracking of oil-derived naphtha. Direct conversion of propane into propylene may be a more attractive alternative. Specifically, propane dehydrogenation (DH) and oxidative dehydrogenation (ODH) are promising for this transformation, albeit only DH has been industrially implemented. However, even the best DH catalysts (Pt-based) still suffer from deactivation. VO x - and BO x -based ODH catalysts result in significant over-oxidation and lack a mechanistic understanding. A common challenge in developing these catalysts is the broad distribution of surface species caused by the use of non-ordered catalyst supports. This hampers clear structure-performance correlations. Recent progress in the preparation of well-defined active sites on ordered supports has brought about improved catalysts, as well as fundamental insight into the working mechanism. This review will highlight recent advancements in the development of these catalysts and provide direction on the use of ordered supports for propane upgrading.
The structural elucidation of catalyst active sites in heterogeneous catalysts when supported by traditional metal oxides remains a challenge despite the advanced characterization techniques that have been developed. The catalyst-deposition-site nonuniformity in metal oxides inhibits clear structural characterization through bulk spectroscopic methods and rules out the use of single-crystal X-ray diffraction. However, for metal-organic framework (MOF)-supported catalysts, the crystallinity and uniform structures of the underlying support enhance our ability to identify the precatalyst and catalytically active sites and open the door to using single-crystal X-ray diffraction coupled with spectroscopy under reaction conditions. Additionally, the use of in situ X-ray absorption spectroscopy identifies the catalytically active site in diethylaluminum chloride (DEAC)-pretreated Cr-SIM-NU-1000 to be a Cr-ethyl when used for ethylene polymerization. Further kinetic experiments elucidate the effects of ethylene pressure, temperature, catalyst loading, and cocatalyst loading, furthering mechanistic knowledge and helping to deconvolute the structure-function relationship.
A layered catalyst structure for purifying an exhaust gas stream includes a catalyst support and a palladium catalyst layer including an atomic dispersion of palladium ions electrostatically adsorbed onto an exterior surface of the catalyst support. The catalyst support includes an alumina substrate, a first ceria layer disposed on and extending substantially continuously over the alumina substrate, and a second colloidal ceria layer formed directly on the first ceria layer over the alumina substrate. The palladium catalyst layer is formed on the exterior surface of the catalyst support by applying a palladium-containing precursor solution to the exterior surface of the catalyst support and then heating the catalyst support and the palladium-containing precursor solution. The palladium-containing precursor solution includes a positively charged palladium complex in an aqueous medium and has a pH greater than a point of zero charge of the second colloidal ceria layer.
Surface modification via grafting of organic moieties on a Lewis acid catalyst (silica supported Ti catalyst, Ti-SiO 2 ) alters the activation of H 2 O 2 in vapor-phase cyclohexene epoxidation. Grafting a fluorous group (1H,1H-perfluoro-octyl) suppresses activity of Ti-SiO 2 . Conversely, grafting either a nonpolar group (octyl) or a polar aprotic group (triethylene glycol monomethyl ether) enhances rates and shifts selectivity toward trans-1,2-cyclohexanediol.
Subnanometer catalysts offer high noble metal utilization and superior performance for several reactions. However, understanding their structures and properties on an atomic scale under working conditions is challenging due to the large configurational space. Here, we introduce an efficient multiscale framework to predict their stability exposed to an adsorbate. The framework integrates a comprehensive toolset including density functional theory (DFT) calculations, cluster expansion, machine learning, and structure optimization. The end-to-end machine-learning workflow guides DFT data generation and enables significant computational acceleration. We demonstrate the approach for CO-adsorbed Pdn (n = 1–55) clusters on CeO 2 (111). Simulation results reveal that CO can facilitate restructuring by stabilizing smaller planar structures and bilayer structures of specific intermediate sizes, consistent with experimental reports. Metal–support interactions, preferential CO adsorption, and metal nuclearity and structure control catalyst stability. As a result, the framework allows automatic discovery of stable catalyst structures and a systematic strategy to exploit properties in the subnanometer scale.
The stability of Ru-based catalysts under harsh electrochemical conditions is a critical challenge limiting their practical application in energy conversion systems. In this study, Ru catalysts supported on ZrO 2-x , CeO 2-x , and ZrCeO 2-x are synthesized via pyrolysis of metal-organic frameworks (MOFs) and systematically evaluated to elucidate the role of support interactions on catalytic performance and durability. Advanced characterization techniques, including HR-TEM, XRD, XPS, and EXAFS, revealed that Ru-ZrCeO 2-x exhibited superior structural stability compared to Ru-ZrO 2-x and Ru-CeO 2-x , particularly under high-potential sweep (HPS) conditions. The incorporation of Ce into ZrO 2-x is shown to stabilize oxygen vacancies and enhance the interaction between Ru catalyst and the support, thereby mitigating catalyst degradation. Density functional theory (DFT) calculations further confirmed that Ce doping decreases formation energy of the oxygen vacancy, providing a thermodynamically favorable environment for Ru stabilization. This work demonstrates the promise of ZrCeO 2-x as a robust support material for Ru-based catalysts, advancing their potential for durable and efficient energy applications.
Atomically dispersed Cu catalyst was designed for highly efficient hydroxylation of aryl iodides under mild conditions.
Sintering poses a significant challenge to achieving the long-term stability of supported metal catalysts under reaction conditions. Here, in this study, we report a low-temperature catalyst redispersion mechanism, in which platinum single atoms, which aggregate into nanoparticles under Reverse Water Gas Shift (RWGS) conditions at elevated temperatures, fragment into atomically dispersed species upon cooling. Using multimodal operando characterization combined with first-principles theoretical modeling, we track the structural evolution of Pt single atoms supported on ceria nanodomes, deposited either on ceria or ceria–titania mixed oxides. We find that fragmentation is more pronounced when cooling occurs under RWGS conditions compared to CO alone, owing to a synergistic interplay of the effects of H 2 , CO 2 , and CO. The support architecture has a strong influence on the extent of redispersion: while CO alone induces fragmentation on ceria, interfacial confinement and vacancy pinning at the ceria–titania interface suppress restructuring. In contrast, RWGS conditions overcome these barriers, enabling redispersion across both supports. These findings point toward a pathway for catalyst stabilization via reaction-induced redispersion under mild conditions.
We report synthesis, characterization, and catalyst performance data for supported metal catalysts, primarily those consisting of noble metals on metal oxide and zeolite supports.
Abstract The availability of durable, high‐performance electrocatalysts for the hydrogen oxidation reaction (HOR) is currently a constraint for anion‐exchange membrane fuel cells (AEMFCs). Herein, a rapid microwave‐assisted synthesis method is used to develop a core–shell catalyst support based on a hydrogenated TiO 2 /carbon for PtRu nanoparticles (NPs). The hydrogenated TiO 2 provides a strong metal‐support interaction with the PtRu NPs, which improves the catalyst's oxophilicity and HOR activity compared to commercial PtRu/C and enables greater size control of the catalyst NPs. The as‐synthesized PtRu/TiO 2 /C‐400 electrocatalyst exhibits respectable performance in an AEMFC operated at 80 °C, yielding the highest current density (up to 3× higher) within the catalytic region (compared at 0.80–0.90 V) and voltage efficiency (68%@ 0.5 A cm −2 ) values in the compared literature. In addition, the cell demonstrates promising short‐term voltage stability with a minor voltage decay of 1.5 mV h −1 . This “first‐of‐its‐kind in alkaline” work may open further research avenues to develop rapid synthesis methods to prepare advanced core–shell metal‐oxide/carbon supports for electrocatalysts for use in the next‐generation of AEMFCs with potential applicability to the broader electrochemical systems research community.
Supported metal nanoparticle catalysts have become increasingly crucial for many catalytic applications. However, long-term catalyst stability remains a problem due to catalyst deactivation caused by coke formation and sintering. The deposition of a thin overcoating via atomic layer deposition (ALD) onto metal-supported nanoparticles has shown to greatly inhibit catalyst deactivation. This work utilizes a model catalyst system comprised of Pt nanoparticles supported on Al 2 O 3 to demonstrate the effect of an atomically thin overcoating on supported metal nanoparticles. Continuous operando small-angle X-ray scattering (SAXS) and X-ray absorption near edge spectroscopy (XANES) monitor structural and electronic changes to the catalyst and overcoating during calcination. SAXS data fitting reveals the formation of nanopores in the overcoating at high temperatures, while XANES monitors the oxidation state of the Pt catalyst. Herein, the usefulness of combined X-ray techniques is demonstrated to characterize supported metal catalysts to further understanding of the synergistic effects of the ALD overcoating to aid in the design of new catalyst materials.
Effective synthesis and application of single-atom catalysts on supports lacking enough defects remain a significant challenge in environmental catalysis. Herein, we present a universal defect-enrichment strategy to increase the surface defects of CeO 2 -based supports through H 2 reduction pretreatment. The Pt catalysts supported by defective CeO 2 -based supports, including CeO 2 , CeZrO x , and CeO 2 /Al 2 O 3 (CA), exhibit much higher Pt dispersion and CO oxidation activity upon reduction activation compared to their counterpart catalysts without defect enrichment. Specifically, Pt is present as embedded single atoms on the CA support with enriched surface defects (CA-HD) based on which the highly active catalyst showing embedded Pt clusters (Pt C ) with the bottom layer of Pt atoms substituting the Ce cations in the CeO 2 surface lattice can be obtained through reduction activation. Embedded PtC can better facilitate CO adsorption and promote O 2 activation at Pt C –CeO 2 interfaces, thereby contributing to the superior low-temperature CO oxidation activity of the Pt/CA-HD catalyst after activation.
Supported iridium complexes, Ir(C 2 H 4 ) 2 /support, were characterized by X-ray absorption spectroscopy during a temperature ramp to 120 °C in flowing H 2 . Iridium in complexes bonded to weak and moderate electron-donor supports, SiO 2 and γ-Al 2 O 3 , underwent aggregation, forming nanoparticles and clusters, respectively. When the support was a strong electron-donor (MgO), iridium remained site-isolated. Density functional theory calculations confirm the dependence of iridium–support bond strength on the support’s electron-donor character. Coating the SiO 2 -supported complexes with 1-n-ethyl-3-methyl-imidazolium acetate enhanced electron density on the iridium, hindering its aggregation. Finally, these results demonstrate opportunities for stabilizing atomically dispersed supported noble metals under reducing conditions by choice of support/ionic liquid sheath combinations.
This review summarizes the recent literature reports on the development of zeolite supported Pd catalysts for the complete oxidation of methane. In-depth analysis reveals that different types of zeolite framework structures, regardless of the dimensionality, pore opening structure, and channel size, have little influence on the methane oxidation activity or the on-stream stability of the supported Pd catalysts. In contrast, the Si/Al ratio of a zeolite support plays a critical role. Both the catalytic activity and the on-stream stability of a Pd/zeolite catalyst increase with the increase of the Si/Al ratio. Catalysts supported on siliceous zeolites consistently show excellent light-off activity and remarkable on-stream stability whether in a dry or wet feed. Silanol nest defect sites in a siliceous zeolite are proposed to be the anchoring sites promoting the formation and minimizing the sintering of finely dispersed Pd nanoparticles. Remaining challenges in overcoming the sulfur poisoning effect are discussed.