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At least 163 records · Page 9

Precise Identification and Characterization of Catalytically Active Sites on the Surface of γ-Alumina

γ-alumina is one of the oldest and most important commercial catalytic materials with high surface area and stability. These attributes enabled its use as the first commercial large-scale heterogeneous catalyst for ethanol dehydration. Despite progress in materials characterization the nature of the specific sites on the surface of γ-alumina that are responsible for its unique catalytic properties has remained obscure and controversial. By using combined infrared spectroscopy, electron microscopy and solid-state nuclear magnetic resonance measurements we identify the octahedral, amphoteric (O) 5 Al(VI)-OH sites on the (100) segments of massively restructured (110) facets on typical rhombus-platelet γ-alumina as well as the (100) segments of irrational surfaces (invariably always present in all γ-alumina samples) responsible for its unique catalytic activity. Such (O) 5 Al(VI)-OH sites are also present on the macroscopically defined (100) facets of γ-alumina with elongated/rod-like geometry. The mechanism by which these sites lose -OH groups upon thermal dehydroxylation resulting in coordinatively unsaturated penta-coordinate Al +3 O 5 sites is clarified. These coordinatively unsaturated penta-coordinate Al sites produce well-defined thermally stable Al-carbonyl complexes. Overall, our findings contribute to the understanding of the nature of coordinatively unsaturated Al sites on the surface of γ-alumina and their role as catalytically active sites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structure of Deep Eutectic Solvents (DESs): What We Know, What We Want to Know, and Why We Need to Know It

We report deep eutectic solvents (DESs) are a tunable class of solvents with many advantageous properties including good thermal stability, facile synthesis, low vapor pressure, and low-to-negligible toxicity. DESs are composed of hydrogen bond donors and acceptors that, when combined, significantly decrease the freezing point of the resulting solvent. DESs have distinct interfacial and bulk structural heterogeneity compared to traditional solvents, in part due to various intramolecular and intermolecular interactions. Many of the physiochemical properties observed for DESs are influenced by structure. However, our understanding of the interfacial and bulk structure of DESs is incomplete. To fully exploit these solvents in a range of applications including catalysis, separations, and electrochemistry, a better understanding of DES structure must be obtained. In this Perspective, we provide an overview of the current knowledge of the interfacial and bulk structure of DESs and suggest future research directions to improve our understanding of this important information.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Plasma catalysis: separating plasma and surface contributions for an Ar/N 2 /O 2 atmospheric discharge interacting with a Pt catalyst

Atmospheric pressure non-equilibrium plasmas can form nitrogen oxide (NO x ) compounds directly from nitrogen and oxygen without a catalyst, and at lower catalyst temperatures than would be possible without plasma. In this work, the oxidation of plasma-produced NO from an Ar/N 2 /O 2 non-equilibrium atmospheric-pressure plasma-jet (APPJ) over a platinum-on-alumina powder catalyst was investigated with in-situ infrared spectroscopy. Products downstream of the catalyst bed were analyzed along with catalyst surface species. The catalyst was exposed to plasma at both constant temperature and a cyclic temperature ramp in order to study long-lasting and transient surface changes. Primary incident reactive species to the catalyst were assessed to be NO and O 3 . Pt-Al 2 O 3 at 350 °C increased oxidation of NO relative to Al 2 O 3 or an empty chamber. The surface state of Pt-Al 2 O 3 evolves during plasma-effluent exposure and requires upwards of 20 min exposure for stabilization compared to Al 2 O 3 . Once stable surface conditions are achieved, thermal cycling reveals a repeatable hysteresis pattern in downstream products. At low temperature, oxygen and NO x accumulate on the catalyst surface and react at elevated temperatures to form NO 2 . Increasing plasma power and O 2 :N 2 ratio increases the hysteresis of the heating relative to the cooling curves in the pattern of NO 2 formation. The limitation on NO oxidation at high temperatures was assessed to be Pt-O which is depleted as the catalyst is heated. Once stored species have been depleted, NO oxidation rates are determined by incoming reactants. Two overlapping NO oxidation patterns are identified, one determined by surface reactants formed at low temperature, and the other by reactants arriving at the surface at high temperature. As a result, the plasma is responsible for providing the reactants to the catalyst surface, while the catalyst enables reaction at high temperature or storage at low temperature for subsequent reaction.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Peroxide-Selective Reduction of O 2 at Redox-Inactive Rare-Earth(III) Triflates Generates an Ambiphilic Peroxide

Metal peroxides are key species involved in a range of critical biological and synthetic processes. Rare-earth (group III and the lanthanides; Sc, Y, La–Lu) peroxides have been implicated as reactive intermediates in catalysis; however, reactivity studies of isolated, structurally characterized rare-earth peroxides have been limited. Herein, we report the peroxide-selective (93–99% O22-) reduction of dioxygen (O 2 ) at redox-inactive rare-earth triflates in methanol using a mild metallocene reductant, decamethylferrocene (Fc*). The first molecular praseodymium peroxide ([Pr III 2( O 2 2- )(18C6) 2 (EG)2][OTf]4; 18C6 = 18-crown-6, EG = ethylene glycol, - OTf = - O 3 SCF 3 ; 2-Pr) was isolated and characterized by single-crystal X-ray diffraction, Raman spectroscopy, and NMR spectroscopy. 2-Pr displays high thermal stability (120 °C, 50 mTorr), is protonated by mild organic acids [pK a1 (MeOH) = 5.09 ± 0.23], and engages in electrophilic (e.g., oxygen atom transfer) and nucleophilic (e.g., phosphate-ester cleavage) reactivity. Our mechanistic studies reveal that the rate of oxygen reduction is dictated by metal-ion accessibility, rather than Lewis acidity, and suggest new opportunities for differentiated reactivity of redox-inactive metal ions by leveraging weak metal–ligand binding events preceding electron transfer.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Coherent charge hopping suppresses photoexcited small polarons in ErFeO 3 by antiadiabatic formation mechanism

Polarons are prevalent in condensed matter systems with strong electron-phonon coupling. The adiabaticity of the polaron relates to its transport properties and spatial extent. To date, only adiabatic small polaron formation has been measured following photoexcitation. The lattice reorganization energy is large enough that the first electron–optical phonon scattering event creates a small polaron without requiring substantial carrier thermalization. We measure that frustrating the iron-centered octahedra in the rare-earth orthoferrite ErFeO 3 leads to antiadiabatic polaron formation. Coherent charge hopping between neighboring Fe 3+ –Fe 2+ sites is measured with transient extreme ultraviolet spectroscopy and lasts several picoseconds before the polaron forms. The resulting small polaron formation time is an order of magnitude longer than previous measurements and indicates a shallow potential well, even in the excited state. The results emphasize the importance of considering dynamic electron-electron correlations, not just electron-phonon–induced lattice changes, for small polarons for transport, catalysis, and photoexcited applications.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Opportunities for Catalytic Reactions and Materials in Buildings

Residential and commercial buildings are responsible for over 30% of global final energy consumption and accounts for ~40% of annual direct and indirect greenhouse gas emissions. Energy efficient and sustainable technologies are necessary to not only lower the energy footprint but also lower the environmental burden. Many proven and emerging technologies are being pursued to meet the ever-increasing energy demand. Catalytic science has a significant new role to play in helping address sustainable energy challenges, particularly in buildings, compared to transportation and industrial sectors. Thermally driven heat pumps, dehumidification, cogeneration, thermal energy storage, carbon capture and utilization, emissions suppression, waste-to-energy conversion, and corrosion prevention technologies can tap into the advantages of catalytic science in realizing the full potential of such approaches, quickly, efficiently, and reliably. Catalysts can help increase energy conversion efficiency in building related technologies but must utilize low cost, easily available and easy-to-manufacture materials for large scale deployment. This entry presents a comprehensive overview of the impact of each building technology area on energy demand and environmental burden, state-of-the-art of catalytic solutions, research, and development opportunities for catalysis in building technologies, while identifying requirements, opportunities, and challenges.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Plasma catalytic ammonia synthesis on Ni nanoparticles: The size effect

Herein we demonstrate the synthesis of ammonia via atmospheric DBD plasma discharge over nickel nanoparticles supported on silica. We evaluated the performance of nickel nanoparticles with average sizes of 5.6nm and 13.5 nm. The smallest nanoparticle size sample resulted in an ammonia synthesis rate at least 2 times higher than that of the larger nanoparticle size sample and nickel bulk at equimolar composition. This allowed us to observe experimentally, for the first time, the size effect in the area of plasma catalysis. Moreover, the presented results allowed us to investigate a hydrogen sink metal such as nickel under atmospheric plasma conditions and determine the gas composition that resulted beneficial for this surface chemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Preparation of ternary hydrophobic magnetic deep eutectic solvents and an investigation into their physicochemical properties

Hydrophobic magnetic deep eutectic solvents (HMDESs) are considered a subclass of DESs comprised of a hydrogen bond acceptor (HBA), hydrogen bond donor (HBD), and a metal halide salt. These DESs can be easily manipulated by an external magnet and employed in numerous applications including liquid–liquid extractions and catalysis. In this work, a total of forty-six (46) HMDESs were prepared and their physicochemical properties studied. Six structurally unique ionic and non-ionic HBAs were combined with lanthanide and transition metal halide salts and twelve different HBDs to prepare room temperature eutectic solvents. The viscosities of HMDESs ranged from 46 centipoise (cP) to 124,600 cP at 23 °C. Their magnetic susceptibilities, studied by superconducting quantum interference device (SQUID) magnetometry and a magnetic susceptibility balance, varied from 3.03 Bohr magnetons (μB) to 9.32 μB when the type of metal halide salt and its molar ratio were varied. Thermal stabilities ranged from 151.1 °C to 308.5 °C at 5% mass loss. Further, all HMDESs comprised of ionic HBA were observed to be insoluble in hexane. This study demonstrates that the physicochemical properties of HMDESs can easily be tailored by varying the DES constituents as well as their molar ratio. The structural tunability of these solvents make them highly attractive candidates for a plethora of applications ranging from extractions to electrochromic applications, where HMDESs can be easily manipulated by an external magnetic field.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nature of Reactive Hydrogen for Ammonia Synthesis over a Ru/C12A7 Electride Catalyst

Recently, there have been renewed interests in exploring new catalysts for ammonia synthesis under mild conditions. Electride-based catalysts are among the emerging ones. Ruthenium particles supported on an electride composed of a mixture of calcium and aluminum oxides (C12A7) have attracted great attention for ammonia synthesis due to their facile ability in activating N2 under ambient pressure. However, the exact nature of the reactive hydrogen species and the role of electride support still remain elusive for this catalytic system. Here, we report for the first time that the surface-adsorbed hydrogen, rather than the hydride encaged in the C12A7 electride, plays a major role in ammonia synthesis over the Ru/C12A7 electride catalyst with the aid of in situ neutron scattering techniques. Combining in situ neutron diffraction, inelastic neutron spectroscopy, density functional theory (DFT) calculation, and temperature-programmed reactions, the results provide direct evidence for not only the presence of encaged hydrides during ammonia synthesis but also the strong thermal and chemical stability of the hydride species in the Ru/C12A7 electride. Steady state isotopic transient kinetic analysis (SSITKA) of ammonia synthesis showed that the coverage of reactive intermediates increased significantly when the Ru particles were promoted by the electride form (coverage up to 84%) of the C12A7 support rather than the oxide form (coverage up to 15%). Such a drastic change in the intermediate coverage on the Ru surface is attributed to the positive role of electride support where the H2 poisoning effect is absent during ammonia synthesis over Ru. The finding of this work has significant implications for understanding catalysis by electride-based materials for ammonia synthesis and hydrogenation reactions in general.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Self-seeded growth of very large open-structured zeolite nanosheet assemblies with extraordinary micropore accessibility

Zeolite nanosheets (ZNs) offer improved micropore accessibilities and transport properties for enhanced molecular catalysis and separations. However, practical application of the ZN materials is hampered by the lack of efficient synthesis methods. Here, in this work, a ZN self-seeded method is demonstrated for single-step reproduction of flower-like assemblies of very large MFI ZN plates. The ZN plates are ~60 nm-thick stacks of 4-nm-thick single-crystal sheets. The ZN flower growth involves terrace nucleation on the seed surfaces and subsequent ZN epitaxial growth in [010] orientation directed by a diquaternary agent. The open architecture of the assemblies prevented collapse and agglomeration of ZNs during thermal activation that effectively preserved the interconnected intra-sheet and inter-sheet micropore system. Thus, the ZN assemblies exhibited markedly enhanced molecular adsorption capacity and transport diffusivity for the probing xylene molecules as compared to the conventional crystals. The ZN assembly and its harvestable very large-sized ZNs have the potential for developing high-performance ZN adsorbents, catalysts, and molecular-sieve membranes.

36 MATERIALS SCIENCE↗

Stabilization of Ultrasmall Platinum Nanoparticles by Nitrogen-Doped Carbon: Implications for Catalysis and Electrocatalysis

Heterogeneous materials comprising platinum nanoparticles on carbon supports have numerous applications including fuel cell electrodes and heterogeneous catalysts. The effective application of these materials for fuel cells and catalysis will be greatly advanced by the ability to control the oxidation and sintering of the nanoparticles by modifications of the carbon support. One attempt of such control has been doping carbon supports with nitrogen. Here, in this work, a cutting-edge, high-sensitivity, in situ XRD instrument, which allows observation of ultrasmall Pt nanoparticles, has been combined with in situ XPS to provide unprecedented clarity in the characterization of supported Pt nanoparticles in oxidizing and high-temperature environments. On a nitrogen-doped carbon support derived from poly-phenylporphyrin, Pt nanoparticles show increased stability to oxidation and thermal sintering. The enhanced Pt–support interaction arising from the N dopant versus the N-free carbon is manifested by (1) decreased initial Pt particle sizes, (2) small particle size at higher surface densities, (3) increased resistance of Pt nanoparticles to oxidation, (4) increased electron binding energy of Pt0, and (5) increased resistance of Pt nanoparticles to sintering. It is expected that the higher stability of Pt on NC will be manifested in higher activity in fuel cells and high-temperature catalytic reactions.

catalytic reactions↗

Circularity in Sequence-Controlled Copolyamides Enabled by Regioselective Enzymatic Hydrolysis

Sequence-controlled polymers enable precise control over macromolecular structures and function, but both their synthesis and end-of-life management remain fundamental challenges. Achieving high sequence fidelity is synthetically demanding, and conventional depolymerization methods lack regioselectivity, leading to irreversible loss of encoded molecular information and limiting polymer circularity. Enzymatic catalysis offers a potential solution by combining substrate specificity with selective bond cleavage. Here, we report the synthesis, characterization, and regioselective enzymatic depolymerization of poly- (X,AMA), a sequence-controlled copolyamide composed of alternating hexamethylenediamine−adipic acid (MA) and pxylylenediamine− adipic acid (XA) repeat units. Poly(X,AMA) was synthesized via solid-state polycondensation (SSP) of sequence-defined oligomers, enabling precise control over repeat-unit order. Polymer microstructure and sequence fidelity were confirmed by 13 C NMR spectroscopy and MALDI−TOF mass spectrometry. Comparison with a statistical copolymer analogue and Nylon-66 demonstrated pronounced differences in crystallinity, morphology, and thermal behavior arising from sequence control. Screening of 96 Nylon hydrolase homologues against poly(X,AMA) revealed strongly enzyme-dependent depolymerization profiles. While tetrad formation was generally favored, enzymes displayed pronounced sequence selectivity, preferentially releasing distinct sequence-defined tetrads XAMA or MAXA. SSP of sequence-defined tetrad MAXA produced a copolyamide with near identical monomer ordering as poly(X,AMA). Computational modeling of enzyme−substrate complexes identified structural features consistent with the observed regioselectivity. Together, these results establish selective enzymatic depolymerization as a viable strategy for the circular recycling of sequence-controlled polymers and provide a foundation for the rational engineering of enzymes for programmable polymer deconstruction.

Amides↗

Pt Catalysts Modified with Manganese Oxide through Atomic Layer Deposition for CO Oxidation: Establishing a Coating Layer above or below Pt

The effect of atomic layer deposition (ALD) of manganese oxide on CO oxidation over Pt/Al2O3 is investigated. Two types of catalysts with a thin MnOx layer coated on or under the Pt nanoparticles (NPs) are prepared, and a pristine Pt/Al2O3 catalyst is used as a reference sample. The addition of the ALD layers improves the catalyst durability and both catalysts with MnOx exhibit greater stability after thermal aging at 1073-K. Besides, MnOx promotes CO oxidation through active Pt-MnOx interfacial sites, showing a reaction rate up to 35-fold faster than that of unmodified Pt. Interestingly, the CO adsorption ability of the Pt catalysts with MnOx overcoats is greatly suppressed after the high-temperature calcination; however, the reaction rate of CO oxidation is still excellent. This phenomenon is because the uniformly covered MnOx with two atomic layers diminishes the exposed Pt surface, but the reaction near the Pt-MnOx interfacial site still occurs. Our results guide the effective use of ALD, which is actively applied to heterogeneous catalysis, and provide a novel direction to control metal-assisted interactions.

36 MATERIALS SCIENCE↗

Microwave-assisted conversion of methane over H-(Fe)-ZSM-5: Evidence for formation of hot metal sites

We report microwave-assisted catalysis offers great promise as an “intensified” technology for chemical processing. The present study investigates microwave-assisted direct conversion of methane with focus on the design and evaluation of microwave-sensitive H-(Fe)ZSM-5 catalysts for the existence of hotspot formation. Isomorphous substituted H-(Fe)ZSM-5 catalysts are tuned to identify key design parameters that control their microwave sensitivity. Increasing the amount of Al and Fe substitution in the zeolite lattice is found to result in higher microwave sensitivity due to improved dielectric properties and hence facilitated microwave heating of the catalyst bed. Comparison between the performance of these catalysts in a conventional thermally-heated (CH) fixed-bed and a microwave (MW) reactor allows identification of the effect of microwave irradiation on the catalyst activity. Methane conversion is drastically enhanced at MW conditions (from 3% at CH conditions to 40% at MW conditions), indicating accelerated methane activation over the metal site and hence suggesting a hot metal site despite much lower catalyst bulk temperature measured in the microwave reactor. The existence of metal hotspot formation is further supported by the reaction product distribution and spent catalyst analysis. At MW conditions, C 2 (ethane and ethylene) and coke (mainly carbon nanotubes and nanofibers) selectivity are much higher at the cost of aromatics make compared to CH conditions. This can be explained by reduced aromatization activity at the Brønsted acid sites of the zeolite due to its lower relative temperature of the zeolite. The much-enhanced metal aggregation observed in the spent catalyst from the MW reactor along with the distribution of coke species further confirms the existence of selective heating (i.e. hotspot formation) occurring at the active metal site in the catalyst at MW conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Microwave-driven heterogeneous catalysis for activation of dinitrogen to ammonia under atmospheric pressure

This paper presents an innovative approach to producing energy-dense, carbon–neutral liquid ammonia as a means for carrying energy. This approach synergistically integrates microwave reaction chemistry with novel heterogeneous catalysis that decouples dinitrogen activation from high-temperature and high-pressure reactions, altering reaction pathways and increasing ammonia formation rate. Results presented here demonstrate that ammonia synthesis can be conducted at 280 ? and ambient pressure to achieve ~1 mmol ammonia/g cat/h over supported ruthenium catalyst systems utilizing microwave irradiation. It is further shown that adding promoter ions such as potassium, cerium, and barium significantly improves the ammonia production rate over undoped ruthenium-based catalysts. This effect could be attributed to enhanced dielectric loss processes that lead to stronger microwave absorption by the catalyst. Measurement of the equilibrium constant under microwave conditions showed a higher ammonia yield than under thermal equilibrium conditions for both the iron- and ruthenium-based catalysts. Finally, this study also illustrates the advantages of using a variable-frequency microwave reactor for ambient-pressure ammonia synthesis. Mechanistically, investigators believed that the oscillating electric fields of the radiation can couple with adsorbed nitrogen on the surface and accelerate its dissociation. Since dinitrogen dissociation on the surface is rate limiting, this effectively accelerates the reaction.

Hu, Jianli (John)↗

Direct observation of the formation and stabilization of metallic nanoparticles on carbon supports

Direct formation of ultra-small nanoparticles on carbon supports by rapid high temperature synthesis method offers new opportunities for scalable nanomanufacturing and the synthesis of stable multi-elemental nanoparticles. However, the underlying mechanisms affecting the dispersion and stability of nanoparticles on the supports during high temperature processing remain enigmatic. In this work, we report the observation of metallic nanoparticles formation and stabilization on carbon supports through in situ Joule heating method. We find that the formation of metallic nanoparticles is associated with the simultaneous phase transition of amorphous carbon to a highly defective turbostratic graphite (T-graphite). Molecular dynamic (MD) simulations suggest that the defective T-graphite provide numerous nucleation sites for the nanoparticles to form. Furthermore, the nanoparticles partially intercalate and take root on edge planes, leading to high binding energy on support. This interaction between nanoparticles and T-graphite substrate strengthens the anchoring and provides excellent thermal stability to the nanoparticles. These findings provide mechanistic understanding of rapid high temperature synthesis of metal nanoparticles on carbon supports and the origin of their stability.

36 MATERIALS SCIENCE↗

Overcoming the phase separation within high-entropy metal carbide by poly(ionic liquid)s

High-entropy crystalline materials are attracting more attention. In principle, high-entropy metal carbides (HMCs) that contain five or more metal ions, possess more negative free energy value during catalysis. But its preparation is challenging because of the immiscibility of multi metal cations in a single carbide solid solution. Here, a rational strategy for preparing HMC is proposed via a coordination-assisted crystallization process in the presence of Br-based poly(ionic liquids). Through this method, Mo 0.2 W 0.2 V 0.2 Cr 0.2 Nb 0.2 C nanoparticles, with a single cubic phase structure, incorporated on porous carbon, are obtained (HMC@NC). By combination of well dispersed small particle size (~4 nm), high surface area (~270 m 2 g –1 ), and high-entropy phase, HMC@NC can function as a promising catalyst for the dehydrogenation of ethylbenzene. Here, unexpected activity (EB conv.: 73%) and thermal stability (>100 h on steam) at 450 °C are observed. Such a facile synthetic strategy may inspire the fabrication of other types of HMCs for more specific tasks.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Designing Sites in Heterogeneous Catalysis: Are We Reaching Selectivities Competitive With Those of Homogeneous Catalysts?

A critical review of different prominent nanotechnologies adapted to catalysis is provided, with focus on how they contribute to the improvement of selectivity in heterogeneous catalysis. Ways to modify catalytic sites range from the use of the reversible or irreversible adsorption of molecular modifiers to the immobilization or tethering of homogeneous catalysts and the development of well-defined catalytic sites on solid surfaces. The latter covers methods for the dispersion of single-atom sites within solid supports as well as the use of complex nanostructures, and it includes the post-modification of materials via processes such as silylation and atomic layer deposition. All these methodologies exhibit both advantages and limitations, but all offer new avenues for the design of catalysts for specific applications. Because of the high cost of most nanotechnologies and the fact that the resulting materials may exhibit limited thermal or chemical stability, they may be best aimed at improving the selective synthesis of high value-added chemicals, to be incorporated in organic synthesis schemes, but other applications are being explored as well to address problems in energy production, for instance, and to design greener chemical processes. Finally, the details of each of these approaches are discussed, and representative examples are provided. We conclude with some general remarks on the future of this field.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗