Methane-H2S Reforming Catalyzed by Carbon and Metal Sulfide Stabilized Sulfur Dimers.

H2S reforming of methane (HRM) provides a potential strategy to directly utilize sour natural gas for the production of COx-free H2 and sulfur chemicals. Several carbon allotropes were found to be active and selective for HRM, while the additional presence of transition metals led to further rate enhancements and outstanding stability (e.g., Ru supported on carbon black). Most metals are transformed to sulfides, but the carbon supports prevent sintering under the harsh reaction conditions. Supported by theoretical calculations, kinetic and isotopic investigations with representative catalysts showed that H2S decomposition and the recombination of surface H atoms are quasi-equilibrated, while the first C-H bond scission is the kinetically relevant step. Theory and experiments jointly establish that dynamically formed surface sulfur dimers are responsible for methane activation and catalytic turnovers on sulfide and carbon surfaces that are otherwise inert without reaction-derived active sites.

Cu-OFF/ERI Zeolite: Intergrowth Structure Synergistically Boosting Selective Catalytic Reduction of NOx with NH3.

Cu-SSZ-13 has been commercialized for selective catalytic reduction with ammonia (NH3-SCR) to remove NOx from diesel exhaust. As its synthesis usually requires toxic and costly organic templates, the discovery of alternative Cu-based zeolite catalysts with organotemplate-free synthesis and comparable or even superior NH3-SCR activity to that of Cu-SSZ-13 is of great academic and industrial significance. Herein, we demonstrated that Cu-T with an intergrowth structure of offretite (OFF) and erionite (ERI) synthesized by an organotemplate-free method showed better catalytic performance than Cu-ERI and Cu-OFF as well as Cu-SSZ-13. Structure characterizations and density functional theory calculations indicated that the intergrowth structure promoted more isolated Cu2+ located at the 6MR of the intergrowth interface, resulting in a better hydrothermal stability of Cu-T than Cu-ERI and Cu-OFF. Strikingly, the low-temperature activity of Cu-T significantly increased after hydrothermal aging, while that of Cu-ERI and Cu-OFF substantially decreased. Based on in situ diffuse reflectance infrared Fourier transform spectra analysis and density functional theory calculations, the reason can be attributed to the fact that NH4NO3 formed on the CuxOy species within ERI polymorph of Cu-T underwent a fast SCR reaction pathway with the assistance of Brønsted acid sites at the intergrowth interfaces under standard SCR reaction conditions. Significantly, Cu-T exhibited a wider temperature window at a catalytic activity of over 90% than Cu-SSZ-13 (175-550 vs 175-500 °C for fresh and 225-500 vs 250-400 °C for hydrothermal treatment). This work provides a new direction for the design of high-performance NH3-SCR catalysts in terms of the interplay of the intergrowth structure of zeolites.

Tricoordinated Single-Atom Cobalt in Zeolite Boosting Propane Dehydrogenation.

Propane dehydrogenation (PDH) reaction has emerged as one of the most promising propylene production routes due to its high selectivity for propylene and good economic benefits. However, the commercial PDH processes usually rely on expensive platinum-based and poisonous chromium oxide based catalysts. The exploration of cost-effective and ecofriendly PDH catalysts with excellent catalytic activity, propylene selectivity, and stability is of great significance yet remains challenging. Here, we discovered a new active center, i.e., an unsaturated tricoordinated cobalt unit (≡Si-O)CoO(O-Mo) in a molybdenum-doped silicalite-1 zeolite, which afforded an unprecedentedly high propylene formation rate of 22.6 molC3H6 gCo-1 h-1 and apparent rate coefficient of 130 molC3H6 gCo-1 h-1 bar-1 with >99% of propylene selectivity at 550 °C. Such activity is nearly one magnitude higher than that of previously reported Co-based catalysts in which cobalt atoms are commonly tetracoordinated, and even superior to that of most of Pt-based catalysts under similar operating conditions. Density functional theory calculations combined with the state-of-the-art characterizations unravel the role of the unsaturated tricoordinated Co unit in facilitating the C-H bond-breaking of propane and propylene desorption. The present work opens new opportunities for future large-scale industrial PDH production based on inexpensive non-noble metal catalysts.

Phenol hydrogenation over H-MFI zeolite encapsulated platinum nanocluster catalyst.

The development of catalysts with high activity and selectivity is of paramount importance for the industrial conversion of biomass. One crucial reaction in this process is the hydrogenation of phenol, a key component of phenolic resins in biomass, into cyclohexanone and cyclohexanol. In this study, density functional theory (DFT) calculations were utilized to examine phenol hydrogenation reaction mechanisms over a platinum (Pt) nanocluster encapsulated in the H-MFI zeolite, e.g., Pt6@H-MFI. Various anchoring positions of the Pt6 nanocluster on the H-MFI framework and the adsorption configurations of phenol on the Pt6@H-MFI were firstly determined. DFT calculation results demonstrate that, compared to the Pt surface, the Pt6@H-MFI catalyst shows high hydrogenation activity with a notable selectivity towards cyclohexanol. The pathway leading to the formation of cyclohexanol is both kinetically and thermodynamically more favorable over the pathway leading to the formation of cyclohexanone. The present work offers significant contributions to the strategic development of catalysts consisting of metal nanoclusters encapsulated within zeolite frameworks.

Confinement of CsPbBr3 Perovskite Nanocrystals into Extra-large-pore Zeolite for Efficient and Stable Photocatalytic Hydrogen Evolution.

Metal halide perovskites (MHPs), renowned for their outstanding optoelectronic properties, hold significant promise as photocatalysts for hydrogen evolution reaction (HER). However, the low stability and insufficient exposure of catalytically active sites of bulky MHPs seriously impair their catalytic efficiency. Herein, we utilized an extra-large-pore zeolite ZEO-1 (JZO) as a host to confine and stabilize the CsPbBr3 nanocrystals (3.4 nm) for boosting hydrogen iodide (HI) splitting. The as-prepared CsPbBr3@ZEO-1 featured sufficiently exposed active sites, superior stability in acidic media, along with intrinsic extra-large pores of ZEO-1 that were favorable for molecule/ion adsorption and diffusion. Most importantly, the unique nanoconfinement effect of ZEO-1 led to the narrowing of the band gap of CsPbBr3, allowing for more efficient light utilization. As a result, the photocatalytic HER rate of the as-prepared CsPbBr3@ZEO-1 photocatalyst was increased to 1734 µmol ⋅ h-1 ⋅ g-1 (CsPbBr3) under visible light irradiation compared with bulk CsPbBr3 (11 µmol ⋅ h-1 ⋅ g-1 (CsPbBr3)), and the long-term durability (36 h) can be achieved. Furthermore, Pt was incorporated with well-dispersed CsPbBr3 nanocrystals into ZEO-1, resulting in a significant enhancement in activity (4826 µmol ⋅ h-1 ⋅ g-1 (CsPbBr3)), surpassing most of the Pt-integrated perovskite-based photocatalysts. Density functional theory (DFT) calculations and charge-carrier dynamics investigation revealed that the dramatically boosted photocatalytic performance of Pt/CsPbBr3@ZEO-1 could be attributed to the promotion of charge separation and transfer, as well as to the substantially lowered energy barrier for HER. This work highlights the advantage of extra-large-pore zeolites as the nanoscale platform to accommodate multiple photoactive components, opening up promising prospects in the design and exploitation of novel zeolite-confined photocatalysts for energy harvesting and storage.

Complete Metal Recycling from Lithium-Ion Batteries Enabled by Hydrogen Evolution Catalyst Reconstruction.

Mass adoption of electric vehicles and the depletion of finite metal resources make it imperative to recycle lithium-ion batteries (LIBs). However, current recycling routes of pyrometallurgy and hydrometallurgy are mainly developed for LiCoO2 and suffer from great energy inputs and extensive processing; thus, alternative versatile and green approaches are in urgent demand. Here, we report an ingenious and versatile strategy for recycling LIBs via catalyst reconstruction, using hydrogen evolution reaction as a proof of concept. Layered, spinel, and polyanion oxide cathode materials, as catalysts, are structurally transformed into hydroxides assisted by protons or hydroxide ions, facilitating complete metal extraction (e.g., Li, Co, Ni, Mn, Fe) with high leaching efficiencies approaching 100%. This recycling method is generally applicable to almost all commercial cathode systems and extended to actual spent pouch cells. Such a green hydrogen coupling approach provides a versatile and sustainable alternative to conventional approaches and has a broad impact beyond battery recycling.

Silanol-Engineered Nonclassical Growth of Zeolite Nanosheets from Oriented Attachment of Amorphous Protozeolite Nanoparticles.

Zeolite nonclassical growth via particle attachment has been proposed for two decades, yet the attachment mechanism and kinetic regulation remain elusive. Here, nonclassical growth of an MFI-type zeolite has been achieved by using amorphous protozeolite (PZ) nanoparticles containing encapsulated TPA+ templates and abundant silanols (Si-OH) as sole precursors under hydrothermal conditions. The silanol characteristics of the precursor were studied by two-dimensional (2D) solid-state nuclear magnetic resonance (NMR) correlation spectroscopy, which were proven to play critical roles in determining precursor attachment behavior and crystal growth orientation. Under mechanical ball-milling or tablet-pressing process, pressure drove the fusion of spherical PZ into platelet-like integrated PZ (IPZ) coupled with transformations of external silanols from evenly distributed to curvature-dependent distributed and internal silanols from isolated to spatially proximate. Compared to isolated silanols, the spatially proximate silanols possessed a stronger correlation with TPA+, benefiting the formation of Si-O-Si bonds via silanol condensation. Subsequently, driven by minimization of surface energy, particle attachment of the platelet-like IPZ precursor preferentially occurred at high-curvature surfaces with high-density silanols, leading to anisotropic rates of nonclassical growth and thus the formation of high-aspect-ratio MFI-type zeolite nanosheets. Advanced electron microscopy provided direct evidence of attachment of amorphous IPZ precursors to crystalline intermediate surfaces along the c-axis direction with the formation of amorphous-crystalline interfaces, followed by interface elimination and structural evolution to a single-crystalline phase. Our findings not only unravel the zeolite nonclassical growth mechanism but also reveal the critical role of silanol chemistry in kinetic regulation, which is of great importance for pursuing a tailored zeolite synthesis.

Enabling High-Performance All-Solid-State Batteries via Guest Wrench in Zeolite Strategy.

All-solid-state batteries with a high energy density and safety are desirable candidates for next-generation energy storage applications. However, conventional solid electrolytes for all-solid-state batteries encounter limitations such as poor ionic conduction, interfacial compatibility, instability, and high cost. Herein, taking advantage of the ingenious capability of zeolite to incorporate functional guests in its void space, we present an innovative ionic activation strategy based on the "guest wrench" mechanism, by introducing a pair of cation and anion of LiTFSI-based guest species (GS) into the supercage of the LiX zeolite, to fabricate a zeolite membrane (ZM)-based solid electrolyte (GS-ZM) with high Li ionic conduction and interfacial compatibility. The restriction of zeolite frameworks toward the framework-associated Li ions is significantly reduced through the dynamic coordination of Li ions with the "oxygen wrench" of TFSI- at room temperature as shown by experiments and Car-Parrinello molecular dynamics simulations. Consequently, the GS-ZM shows an ∼100% increase in ionic conductivity compared with ZM and an outstanding Li+ transference number of 0.97. Remarkably, leveraging the superior ionic conduction of GS-ZM with the favorable interface structure between GS-ZM and electrodes, the assembled all-solid-state Li-ion and Li-air batteries based on GS-ZM exhibit the best-level electrochemical performance much superior to batteries based on liquid electrolytes: a capacity retention of 99.3% after 800 cycles at 1 C for all-solid-state Li-ion batteries and a cycle life of 909 cycles at 500 mA g-1 for all-solid-state Li-air batteries. The mechanistic discovery of a "guest wrench" in zeolite will significantly enhance the adaptability of zeolite-based electrolytes in a variety of all-solid-state energy storage systems with high performance, high safety, and low cost.

Theoretical Screening of CO2 Electroreduction over MOF-808-Supported Self-Adaptive Dual-Metal-Site Pairs.

Electrochemical CO2 reduction to transportation fuels and valuable platform chemicals provides a sustainable avenue for renewable energy storage and realizes an artificially closed carbon loop. However, the rational design of highly active and selective CO2 reduction electrocatalysts remains a challenging task. Herein, a series of metal-organic framework (MOF)-supported flexible, self-adaptive dual-metal-site pairs (DMSPs) including 21 pairwise combinations of six transition metal single sites (MOF-808-EDTA-M1M2, M1/M2 = Fe, Cu, Ni, Pd, Pt, Au) for the CO2 reduction reaction (CO2RR) were theoretically screened using density functional theory calculations. Against the competitive hydrogen evolution reaction, MOF-808-EDTA-FeFe and MOF-808-EDTA-FePt were identified as the promising CO2RR electrocatalysts toward C1 and C2 products. The calculated limiting potential for CO2 electroreduction to C2H6 and C2H5OH over MOF-808-EDTA-FeFe is -0.87 V. Compared with an applied potential of -0.56 eV toward CH4 production over MOF-808-EDTA-FeFe, MOF-808-EDTA-FePt exhibits an even better activity for CO2 reduction to C1 products at a limiting potential of -0.35 V. The present work not only identifies promising candidates for highly selective CO2RR electrocatalysts leading to C1 and C2 products but also provides mechanistic insights into the dynamic nature of DMSPs for stabilizing various reaction intermediates in the CO2RR process.

Encapsulation of Palladium Carbide Subnanometric Species in Zeolite Boosts Highly Selective Semihydrogenation of Alkynes.

The selective hydrogenation of alkynes to alkenes is a crucial step in the synthesis of fine chemicals. However, the widely utilized palladium (Pd)-based catalysts often suffer from poor selectivity. In this work, we demonstrate a carbonization-reduction method to create palladium carbide subnanometric species within pure silicate MFI zeolite. The carbon species can modify the electronic and steric characteristics of Pd species by forming the predominant Pd-C4 structure and, meanwhile, facilitate the desorption of alkenes by forming the Si-O-C structure with zeolite framework, as validated by the state-of-the-art characterizations and theoretical calculations. The developed catalyst shows superior performance in the selective hydrogenation of alkynes over mild conditions (298 K, 2 bar H2 ), with 99 % selectivity to styrene at a complete conversion of phenylacetylene. In contrast, the zeolite-encapsulated carbon-free Pd catalyst and the commercial Lindlar catalyst show only 15 % and 14 % selectivity to styrene, respectively, under identical reaction conditions. The zeolite-confined Pd-carbide subnanoclusters promise their superior properties in semihydrogenation of alkynes.

Unveiling Secondary-Ion-Promoted Catalytic Properties of Cu-SSZ-13 Zeolites for Selective Catalytic Reduction of NOx.

The incorporation of secondary metal ions into Cu-exchanged SSZ-13 zeolites could improve their catalytic properties in selective catalytic reduction of NOx with ammonia (NH3-SCR), but their essential roles remain unclear at the molecular level. Herein, a series of Cu-Sm-SSZ-13 zeolites have been prepared by ion-exchanging Sm ions followed by Cu ions, which exhibit superior NH3-SCR performance. The NO conversion of Cu-Sm-SSZ-13 is nearly 10% higher than that of conventional Cu-SSZ-13 (175-250 °C) after hydrothermal ageing, showing an enhanced low-temperature activity. The Sm ions are found to occupy the six-membered rings (6MRs) of SSZ-13 by X-ray diffraction Rietveld refinement and aberration-corrected scanning transmission electron microscopy. The Sm ions at 6MRs can facilitate the formation of more active [ZCu2+(OH)]+ ions at 8MRs, as revealed by temperature-programmed reduction of hydrogen. X-ray photoelectron spectroscopy and density functional theory (DFT) calculations indicate that there exists electron transfer from Sm3+ to [ZCu2+(OH)]+ ions, which promotes the activity of [ZCu2+(OH)]+ ions by decreasing the activation energy of the formation of intermediates (NH4NO2 and H2NNO). Meanwhile, the electrostatic interaction between Sm3+ and [ZCu2+(OH)]+ results in a high-reaction energy barrier for transforming [ZCu2+(OH)]+ ions into inactive CuOx species, thus enhancing the stability of [ZCu2+(OH)]+ ions. The influence of the ion-exchanging sequence of Sm and Cu ions into SSZ-13 is further investigated by combining both experiments and theoretical calculations. This work provides a mechanistic insight of secondary ions in regulating the distribution, activity, and stability of Cu active sites, which is helpful for the design of high-performance Cu-SSZ-13 catalysts for the NH3-SCR reaction.

Mechanistic insights into positional and skeletal isomerization of cyclohexene in the H-BEA zeolite.

The isomerization of cycloalkenes via the formation of carbenium cations assisted by the Brønsted acid site (BAS) in zeolites is the vital reaction step in hydrocracking and hydroisomerization processes of the petrochemical industry. To understand the acid-catalyzed positional isomerization and skeletal isomerization of cycloalkenes via carbenium intermediates, a series of ab initio molecular dynamics (AIMD) simulations of cyclohexene within the H-BEA zeolite have been carried out. AIMD simulations combined with the enhanced sampling technique reveal that the half-chair conformer is the most stable conformation for cyclohexene within H-BEA. Free energy landscapes characterizing protonation/deprotonation, positional isomerization, and skeletal isomerization of cyclohexene have been mapped out at 413 K. The free energy barrier for the formation of carbenium is calculated to be 44 kJ mol-1. The skeletal isomerization of cyclohexene to methylcyclopentylium via the protonated cyclopropane transition state involves four stages with a total free energy barrier of 134 kJ mol-1. Further geometrical analysis provides additional information about the structural origin of free energy barriers.

Theoretical characterization of zeolite encapsulated platinum clusters in the presence of water molecules.

Zeolite encapsulated metal clusters have shown high catalytic activity and superior stability due to confinement effects, the synergy between acidic and metal active sites, and strong metal-zeolite interactions. In the present work, density functional theory calculations were employed to study the stability of encapsulated Ptn (n = 1-6) clusters in the zeolitic frameworks including Silicalite-1 and H-MFI. It has been found that the metal-zeolite interaction becomes stronger with the increasing Ptn cluster size for both zeolitic frameworks. The encapsulated Ptn clusters in the vicinity of the Brønsted acid site (BAS) of H-MFI form more stable PtnHx (x = 1, 2) clusters. The presence of water molecules around the encapsulated Pt6 cluster further enhances its stability, while the oxidation states of the encapsulated Ptn cluster are largely affected by the BAS site and the surrounding water molecules. As the water concentration increases, water dissociation becomes more facile on the Pt6@Silicalite-1 cluster while an opposite trend is found over the Pt6H2@H-MFI cluster. The proton of the BAS site can be transferred to the encapsulated Pt6 cluster via a hydronium cluster H+(H2O)n, leading to the formation of the Pt6H2@H-MFI cluster.

Insights into protonation for cyclohexanol/water mixtures at the zeolitic Brønsted acid site.

Proton transfer from Brønsted acid sites (BASs) to alcohol molecules ignites the acid-catalyzed alcohol dehydration reactions. For aqueous phase dehydration reactions in zeolites, the coexisting water molecules around BASs in the zeolite pores significantly affect the alcohol dehydration activity. In the present work, proton transfer processes among the BASs of H-BEA zeolites, the adsorbed cyclohexanol and surrounding water clusters with different sizes up to 8 water molecules were investigated using ab initio molecular dynamics (AIMD) simulations combined with the multiple-walker well-tempered metadynamics algorithm. The plausible proton locations and proton transfer processes were characterized using two/three-dimensional free energy landscapes. The strong proton affinity makes the protonated cyclohexanol stable species until a water trimer is formed. The proton either is shared between protonated cyclohexanol and the water trimer or remains with the water trimer (H7O3+). With a further increase in water concentrations, the proton prefers to remain with the water clusters.

A density functional theoretical study on the stability of Pt clusters in MOF-808.

Metal organic framework (MOF)-encapsulated metal clusters have shown superior catalytic activity due to geometric and electronic properties of metal clusters, which are largely determined by adsorption sites and sizes and morphologies of encapsulated metal clusters. In the present work, anchoring sites, the stability, and the agglomeration probability of Ptn (n = 1-23) clusters over an MOF-808 framework structure were studied using density functional theory calculations and ab initio molecular dynamics simulation. It has been found that Ptn (n = 1-7) clusters bind more strongly at the Zr6 metal node sites than at the interface and linker sites. Upon adsorption, significant amounts of electrons (+0.92 to +1.96 |e|) are transferred from Ptn clusters to the MOF framework. The agglomeration of single Pt1 atoms at the Zr6 metal node to form a Ptn cluster is unlikely, while the agglomeration at the interface or the linker is energetically feasible. Compared with the single Zr6 node, the bonding of Ptn clusters with two Zr6 metal nodes is weaker, with less electron (+0.12 to +0.89 |e|) transfer. Finally, our calculations show that CO adsorption at the single Pt atom is stabilized at the interface site, preventing its further agglomeration with Ptn clusters between the two Zr6 metal nodes.

The shuttling mechanism of foldaxanes: more than just translocation and rotation.

Tailoring the structures of nanomachines to achieve specific functions is one of the major challenges in chemistry. Disentangling the different movements of nanomachines is critical to characterize their functions. Here, the motions within one kind of molecular machine, a foldaxane, composed of a foldamer with a spring-like conformation on an axle have been examined at the molecular level. With the aid of molecular dynamics simulations and enhanced sampling methods, the free-energy landscape characterizing the shuttling of the foldaxane has been drawn. The calculated free-energy barrier, amounting to 20.7 kcal mol-1, is in good agreement with experiments. Further analysis reveals that the predominant contribution to the free-energy barrier stems from the disruption of the hydrogen bonds between the foldamer and the thread. In the absence of hydrogen bonding interactions between the terminals of the foldamer and the thread, shrinkage and swelling movements of the foldamer have been identified and investigated in detail. By deciphering the intricate mechanism of how the foldaxane shuttles, our understanding of motions within molecular machines is expected to be improved, which will, in turn, assist the construction of molecular machines with specific functions.

The Critical Role of Reductive Steps in the Nickel-Catalyzed Hydrogenolysis and Hydrolysis of Aryl Ether C-O Bonds.

The hydrogenolysis of the aromatic C-O bond in aryl ethers catalyzed by Ni was studied in decalin and water. Observations of a significant kinetic isotope effect (kH /kD =5.7) for the reactions of diphenyl ether under H2 and D2 atmosphere and a positive dependence of the rate on H2 chemical potential in decalin indicate that addition of H to the aromatic ring is involved in the rate-limiting step. All kinetic evidence points to the fact that H addition occurs concerted with C-O bond scission. DFT calculations also suggest a route consistent with these observations involving hydrogen atom addition to the ipso position of the phenyl ring concerted with C-O scission. Hydrogenolysis initiated by H addition in water is more selective (ca. 75 %) than reactions in decalin (ca. 30 %).

Genesis and Stability of Hydronium Ions in Zeolite Channels.

The catalytic sites of acidic zeolite are profoundly altered by the presence of water changing the nature of the Brønsted acid site. High-resolution solid-state NMR spectroscopy shows water interacting with zeolite Brønsted acid sites, converting them to hydrated hydronium ions over a wide range of temperature and thermodynamic activity of water. A signal at 9 ppm was observed at loadings of 2-9 water molecules per Brønsted acid site and is assigned to hydrated hydronium ions on the basis of the evolution of the signal with increasing water content, chemical shift calculations, and the direct comparison with HClO4 in water. The intensity of 1H-29Si cross-polarization signal first increased and then decreased with increasing water chemical potential. This indicates that hydrogen bonds between water molecules and the tetrahedrally coordinated aluminum in the zeolite lattice weaken with the formation of hydronium ion-water clusters and increase the mobility of protons. DFT-based ab initio molecular dynamics studies at multiple temperatures and water concentrations agree well with this interpretation. Above 140 °C, however, fast proton exchange between bridging hydroxyl groups and water occurs even in the presence of only one water molecule per acid site.

Entrapped Single Tungstate Site in Zeolite for Cooperative Catalysis of Olefin Metathesis with Brønsted Acid Site.

Industrial olefin metathesis catalysts generally suffer from low reaction rates and require harsh reaction conditions for moderate activities. This is due to their inability to prevent metathesis active sites (MASs) from aggregation and their intrinsic poor adsorption and activation of olefin molecules. Here, isolated tungstate species as single molecular MASs are immobilized inside zeolite pores by Brønsted acid sites (BASs) on the inner surface. It is demonstrated that unoccupied BASs in atomic proximity to MASs enhance olefin adsorption and facilitate the formation of metallocycle intermediates in a stereospecific manner. Thus, effective cooperative catalysis takes place over the BAS-MAS pair inside the zeolite cavity. In consequence, for the cross-metathesis of ethene and trans-2-butene to propene, under mild reaction conditions, the propene production rate over WO x/USY is ca. 7300 times that over the industrial WO3/SiO2-based catalyst. A propene yield up to 79% (80% selectivity) without observable deactivation was obtained over WO x/USY for a wide range of reaction conditions.

Selective Catalytic Reduction over Cu/SSZ-13: Linking Homo- and Heterogeneous Catalysis.

Active centers in Cu/SSZ-13 selective catalytic reduction (SCR) catalysts have been recently identified as isolated Cu2+ and [CuII(OH)]+ ions. A redox reaction mechanism has also been established, where Cu ions cycle between CuI and CuII oxidation states during SCR reaction. While the mechanism for the reduction half-cycle (CuII → CuI) is reasonably well-understood, that for the oxidation half-cycle (CuI → CuII) remains an unsettled debate. Herein we report detailed reaction kinetics on low-temperature standard NH3-SCR, supplemented by DFT calculations, as strong evidence that the low-temperature oxidation half-cycle occurs with the participation of two isolated CuI ions via formation of a transient [CuI(NH3)2]+-O2-[CuI(NH3)2]+ intermediate. The feasibility of this reaction mechanism is confirmed from DFT calculations, and the simulated energy barrier and rate constants are consistent with experimental findings. Significantly, the low-temperature standard SCR mechanism proposed here provides full consistency with low-temperature SCR kinetics.