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At least 91 records · Page 5

Fine-Tuning of Pt Dispersion on Al 2 O 3 and Understanding the Nature of Active Pt Sites for Efficient CO and NH 3 Oxidation Reactions

Fine-tuning the dispersion of active metal species on widely used supports is a research hotspot in the catalysis community, which is vital for achieving a balance between the atomic utilization efficiency and the intrinsic activity of active sites. In this work, using bayerite Al(OH) 3 as support directly or after precalcination at 200 or 550 °C, Pt/Al 2 O 3 catalysts with distinct Pt dispersions from single atoms to clusters (ca. 2 nm) were prepared and evaluated for CO and NH 3 removal. Richer surface hydroxyl groups on AlO x (OH) y support were proved to better facilitate the dispersion of Pt. However, Pt/Al 2 O 3 with relatively lower Pt dispersion could exhibit better activity in CO/NH 3 oxidation reactions. Further reaction mechanism study revealed that the Pt sites on Pt/Al 2 O 3 with lower Pt dispersion could be activated to Pt 0 species much easier under the CO oxidation condition, on which a higher CO adsorption capacity and more efficient O 2 activation were achieved simultaneously. Compared to Pt single atoms, PtO x clusters could also better activate NH 3 into –NH 2 and –HNO species. The higher CO adsorption capacity and the more efficient NH 3 /O 2 activation ability on Pt/Al 2 O 3 with relatively lower Pt dispersion well explained its higher CO/NH 3 oxidation activity. This study emphasizes the importance of avoiding a singular pursuit of single-atom catalyst synthesis and instead focusing on achieving the most effective Pt species on Al 2 O 3 support for targeted reactions. Finally, this approach avoids unnecessary limitations and enables a more practical and efficient strategy for Pt catalyst fabrication in emission control applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Aliovalent Doping of CeO 2 Improves the Stability of Atomically Dispersed Pt

Atomically dispersed supported catalysts hold considerable promise as catalytic materials. The ability to employ and stabilize them against aggregation in complex process environments remains a key challenge to the elusive goal of 100% atom utilization in catalysis. In this work, using a Gd-doped ceria support for atomically dispersed surface Pt atoms, we establish how the combined effects of aliovalent doping and oxygen vacancy generation provide dynamic mechanisms that serve to enhance the stability of supported single atom configurations. Using correlated, in situ X-ray absorption, photoelectron and vibrational spectroscopies for analysis of the samples on the two types of support (with and without Gd doping), we establish that the Pt atoms locate proximal to Gd dopants, forming a speciation that serves to enhance the thermal stability of Pt atoms against aggregation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dynamic Behavior of Platinum Atoms and Clusters in the Native Oxide Layer of Aluminum Nanocrystals

Strong metal–support interactions (SMSIs) are well-known in the field of heterogeneous catalysis to induce the encapsulation of platinum (Pt) group metals by oxide supports through high temperature H 2 reduction. However, demonstrations of SMSI overlayers have largely been limited to reducible oxides, such as TiO 2 and Nb 2 O 5 . In this report we show that the amorphous native surface oxide of plasmonic aluminum nanocrystals (AlNCs) exhibits SMSI-induced encapsulation of Pt following reduction in H 2 in a Pt structure dependent manner. Reductive treatment in H 2 at 300 °C induces the formation of an AlO x SMSI overlayer on Pt clusters, leaving Pt single-atom sites (Ptiso) exposed available for catalysis. The remaining exposed Pt iso species possess a more uniform local coordination environment than has been observed on other forms of Al 2 O 3 , suggesting that the AlO x native oxide of AlNCs presents well-defined anchoring sites for individual Pt atoms. This observation extends our understanding of SMSIs by providing evidence that H 2 -induced encapsulation can occur for a wider variety of materials and should stimulate expanded studies of this effect to include nonreducible oxides with oxygen defects and the presence of disorder. It also suggests that the single-atom sites created in this manner, when combined with the plasmonic properties of the Al nanocrystal core, may allow for site-specific single-atom plasmonic photocatalysis, providing dynamic control over the light-driven reactivity in these systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Designing ultrastable Pt/CeO 2 -Al 2 O 3 nanosheet catalysts for three-way catalysts applications

Designing Rh-free, especially Pt-only, three-way catalysts with improved low-temperature activity/stability is highly desirable. Herein, we demonstrate that ultrastable Pt/CeO 2 -Al 2 O 3 nanosheet catalysts can be obtained based on a Sabatier principle of metal-support interaction. Tuning the surface coverage of penta-site rich γ-Al 2 O 3 nanosheets (AlNS, weak adhesion to Pt) by CeO 2 “nano-islands” (strong adhesion to Pt) can lead to the synthesis of Pt/60 wt.%CeO 2 -AlNS that have lower light-off temperatures for CO, hydrocarbons, and NO compared to conventional Pt/CeO 2 and Pt/Al 2 O 3 catalysts by 100–200°C and a similar performance with the state-of-the-art Rh-based catalyst. Further, incorporating CeO 2 on the surface of AlNS can retard the sintering of CeO 2 during harsh redox hydrothermal aging, associate with the strong interaction between CeO 2 “nano-island” and penta-site rich γ-Al 2 O 3 nanosheets. Moreover, the improved activity/stability of Pt/CeO 2 -AlNS catalysts can be attributed to tuning of the Pt detachment and migration from and back to the CeO 2 “nano-islands”, respectively, that keeps Pt as nanoclusters on CeO 2 , the most active species for three-way catalyst applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Grafting nanometer metal/oxide interface towards enhanced low-temperature acetylene semi-hydrogenation

Metal/oxide interface is of fundamental significance to heterogeneous catalysis because the seemingly “inert” oxide support can modulate the morphology, atomic and electronic structures of the metal catalyst through the interface. The interfacial effects are well studied over a bulk oxide support but remain elusive for nanometer-sized systems like clusters, arising from the challenges associated with chemical synthesis and structural elucidation of such hybrid clusters. We hereby demonstrate the essential catalytic roles of a nanometer metal/oxide interface constructed by a hybrid Pd/Bi 2 O 3 cluster ensemble, which is fabricated by a facile stepwise photochemical method. The Pd/Bi 2 O 3 cluster, of which the hybrid structure is elucidated by combined electron microscopy and microanalysis, features a small Pd-Pd coordination number and more importantly a Pd-Bi spatial correlation ascribed to the heterografting between Pd and Bi terminated Bi 2 O 3 clusters. The intra-cluster electron transfer towards Pd across the as-formed nanometer metal/oxide interface significantly weakens the ethylene adsorption without compromising the hydrogen activation. As a result, a 91% selectivity of ethylene and 90% conversion of acetylene can be achieved in a front-end hydrogenation process with a temperature as low as 44 °C.

36 MATERIALS SCIENCE↗

Mineral catalysis of a potentially prebiotic aldol condensation

Minerals may have played a significant role in chemical evolution. In the course of investigating the chemistry of phosphonoacetaldehyde (PAL), an analogue of glycolaldehyde phosphate, we have observed a striking case of catalysis by the layered hydroxide mineral hydrotalcite ([Mg2Al(OH)6][Cl.nH2O]). In neutral or moderately basic aqueous solutions, PAL is unreactive even at a concentration of 0.1 M. In the presence of a large excess of NaOH (2 M), the compound undergoes aldol condensation to produce a dimer containing a C3-C4 double-bond. In dilute neutral solutions and in the presence of the mineral, however, condensation takes place rapidly, to produce a dimer which is almost exclusively the C2-C3 unsaturated product.

Non-NASA Center↗

Catalytic roles of the AMP at the 3' end of tRNAs

Recent reports suggest that the ribosome retains considerable peptidyl transferase activity even when much of the protein of the ribosome is removed and further suggests that rRNA may be the peptidyl transferase. The work here suggests that the AMP residue at the 3' terminus of each tRNA has some catalytic activity both in the esterification reaction and in forming a pseudopeptide, AcGly, and further suggests that whatever peptidyl transferase is, it finds a cooperative substrate in the aminoacyl-AMP at the 3' terminus of tRNA.

Non-NASA Center↗

Template switching between PNA and RNA oligonucleotides

The origin of the RNA world is not easily understood, as effective prebiotic syntheses of the components of RNA, the beta-ribofuranoside-5'-phosphates, are hard to envisage. Recognition of this difficulty has led to the proposal that other genetic systems, the components of which are more easily formed, may have preceded RNA. This raises the question of how transitions between one genetic system and another could occur. Peptide nucleic acid (PNA) resembles RNA in its ability to form double-helical complexes stabilized by Watson-Crick hydrogen bonding between adenine and thymine and between cytosine and guanine, but has a backbone that is held together by amide rather than by phosphodiester bonds. Oligonucleotides bases on RNA are known to act as templates that catalyse the non-enzymatic synthesis of their complements from activated mononucleotides, we now show that RNA oligonucleotides facilitate the synthesis of complementary PNA strands and vice versa. This suggests that a transition between different genetic systems can occur without loss of information.

NASA Discipline Exobiology↗

Rational design of heterogeneous single-site catalysts via surface organometallic chemistry

Single-site heterogeneous catalysts offer an attractive route to unite the molecular precision of homogeneous catalysis with the durability and practical advantages of solids. Surface organometallic chemistry (SOMC) provides a particularly powerful strategy for this purpose by grafting molecular precursors onto tailored surfaces and converting support functionalities into ligand environments for isolated metal centers. As a result, SOMC brings the language and logic of coordination chemistry to heterogeneous catalysis, where the support becomes an integral part of the active site coordination sphere. This Review surveys recent progress in the rational design of SOMC-derived single-site catalysts, with emphasis on synthetic routes, post synthetic transformations, and the deliberate tuning of catalytic behavior through metal-support interactions. Discussions are made on how support identity, hydroxyl topology, acidity, and redox activity shape the geometry, electronic structure, and oxidation state of supported metal sites, as well as how these factors determine activity, selectivity, and stability. We also examine a central limitation of these systems: despite their molecularly informed design, supported single sites often exist as structurally distributed ensembles rather than uniform species, particularly on amorphous supports. This site heterogeneity, along with catalyst dynamics under operating conditions, remains a major barrier to definitive structure-activity relationships. Therefore, emerging approaches that combine advanced characterization, first-principles modeling, ensemble kinetics, and machine learning to resolve active-site structure and guide catalyst development are highlighted. Together, these advances position SOMC as a versatile coordination chemistry framework for the predictive design of heterogeneous catalysts with well-defined molecularly tailored active sites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Enhancing the Carbon Monoxide Oxidation Performance through Surface Defect Enrichment of Ceria-Based Supports for Platinum Catalyst

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.

36 MATERIALS SCIENCE↗

p-Block Metal Oxide Noninnocence in the Oxygen Evolution Reaction in Acid: The Case of Bismuth Oxide

The Pourbaix diagrams of p-block Pb, Sb, and Bi establish a robust stability for their oxides in acidic solutions. Such oxides have found utility as stable frameworks to support metals that are active for oxygen evolution reaction (OER) catalysis, but they also possess two-electron redox couples, which can potentially engender OER activity. Thus, the use of p-block oxide supports provides an imperative for understanding the OER activity of the unary oxides. Toward this end, we report BiO x films that are able to perform OER catalysis at moderate overpotentials for extended periods of operation (>110 h) in highly acidic solutions (pH 1.0–2.25) with no sign of decreased OER activity during operation at current densities of 1–5 mA cm –2 . X-ray photoelectron spectroscopy (XPS), cyclic voltammetry (CV), and UV-vis spectroelectrochemistry reveal a change in the Bi oxidation state prior to OER catalysis, from predominantly Bi 3+ in the as-deposited films to primarily Bi 5+ in the catalytically active films. Furthermore, this transformation is accompanied by a prominent color change from orange to dark brown. Simulations of the cyclic voltammogram catalytic profiles suggest two OER pathways for BiO x involving Bi IV O x and Bi V O x catalysts with the Bi V O x pathway prevailing after catalyst activation. Together, these results demonstrate the ability of BiO x to facilitate OER in acid with high functional stability and underscore the noninnocent role that p-block metal oxides may play in OER catalysis in acidic media.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The role of Tyr34 in proton coupled electron transfer and product inhibition of manganese superoxide dismutase

Human manganese superoxide dismutase (MnSOD) plays a crucial role in controlling levels of reactive oxygen species (ROS) by converting superoxide (O$^{•–}_{2}$) to molecular oxygen (O 2 ) and hydrogen peroxide (H 2 O 2 ) with proton-coupled electron transfers (PCETs). A key catalytic residue, Tyr34, determines the activity of human MnSOD and also becomes post-translationally inactivated by nitration in various diseases associated with mitochondrial dysfunction. Tyr34 has an unusual pK a due to its proximity to the Mn metal and undergoes cyclic deprotonation and protonation events to promote the electron transfers of MnSOD. Neutron diffraction, X-ray spectroscopy, and quantum chemistry calculations in oxidized, reduced and product inhibited enzymatic states shed light on the role of Tyr34 in MnSOD catalysis. The data identify the contributions of Tyr34 in MnSOD activity that support mitochondrial function and give a thorough characterization of how a single tyrosine modulates PCET catalysis. Product inhibition occurs by an associative displacement mechanism.

60 APPLIED LIFE SCIENCES↗

Ultrathin alumina passivation for improved photoelectrochemical water oxidation catalysis of tin oxide sensitized by a phosphonate-functionalized perylene diimide first without, and then with, CoOy

Previously, a photoanode composed of nanostructured SnO 2 coated with the perylene diimide dye N,N'-bis(phosphonomethyl)-3,4,9,10-perylenediimide (PMPDI) plus photoelectrochemically deposited cobalt oxide (CoO y ) was shown to photoelectrochemically oxidize water at 31 ± 7% faradaic efficiency. A non-ideal part of that prior system is that the addition of the known CoO y water oxidation catalyst (WOC) resulted in a reduction of the total photocurrent rather than the anticipated increase, due to an increase in charge-carrier recombination. Herein, we show deposition of an ultrathin alumina overlayer applied by atomic layer deposition (ALD) on the SnO 2 /PMPDI photoanode can improve the photoactivity and catalytic activity of the system; the addition a ca. 1 nm-thick AlO x layer deposited on a 4000 nm (i.e., 4 micron) thick mesoporous anode system can and does have a positive, 2.5-fold improvement in the steady-state photocurrent with 29 ± 9% faradaic efficiency vs. the control anode without alumina passivation by reducing charge-carrier recombination. Moreover, ALD-deposited AlO x layer does help support the understanding of the “anti-catalysis” of co-depositing a CoO y WOC on the SnO 2 /PMPDI DS-PECs—specifically the picture of direct CoO y –SnO 2 contact-mediated recombination—but that AlO x layer was unable to improve the photocurrent in a net SnO 2 /PMPDI/AlO x (/CoO y ) system. We attribute the lack of a performance enhancement by CoOy WOC to incomplete coverage of each SnO 2 nanoparticle by the AlO x . Overall, we find the addition of an optimized ultrathin AlOx layer (0.6 nm thick; deposited at 85 °C) improves the SnO 2 /PMPDI/AlO x system's photoactivity by a factor of up to ca. 3-fold with reduced recombination. These results document that metal-oxide passivation by low-temperature ALD can be an effective strategy for improving the water oxidation performance of even nanostructured dye sensitized-photoelectrochemical cell.

36 MATERIALS SCIENCE↗

Enhancing the Value of Wasted and Stranded Natural Gas Resources Through Conversion Into Aromatics Using Microwaves

Natural gas flaring results in the waste of significant amounts of valuable domestic energy resources while also producing undesirable environmental impacts. Transforming natural gas into value-added chemicals via direct nonoxidative reactions presents a compelling alternative to flaring. However, traditional thermal reactor systems face challenges due to thermodynamic limitations and poor catalyst stability. Microwave-assisted reactions offer a sustainable, on-demand approach for chemical production from natural gas, suitable for compact, flexible reactor systems at the well-site that can be powered by renewable energy. This method offers a novel, non-traditional approach in catalyst activation and product selectivity compared to a conventional thermal method, potentially leading to faster rates, higher selectivities, and higher conversion efficiencies. Despite these advantages, challenges exist, such as the low microwave-sensitivity of the state-of-the-art zeolite catalyst that is highly active for the methane dehydroaromatization reaction. This presentation will discuss recent research from the National Energy Technology Laboratory concerning microwave-assisted natural gas conversion directly into aromatics. It will address the difficulties with microwave heating of traditional thermochemical catalysts, and the application of Multiphysics modeling to understand temperature and field strength in the reactor, to enhance chemical conversion. The presentation will also cover how heating aids can mitigate heating challenges and transform microwave catalysis into a quasi-thermal kinetic problem. Additionally, catalyst activation and deactivation under microwave conditions will be examined, along with the future outlook and needs for microwave enhanced catalysis applications.

catalysis↗

Size-Dependent Energy of Ni Nanoparticles on Graphene Films on Ni(111) and Adhesion Energetics by Adsorption Calorimetry

The use of carbon supports for late transition-metal nanoparticle catalysts has grown substantially in recent years due to efforts to develop electrocatalysts for clean energy applications and catalysts for new aqueous-phase biomass-related conversions and due to the evolution of new carbon materials with unique properties (e.g., graphene, carbon nanotubes, and so forth). However, much less is known about the bonding energetics of catalytic metal nanoparticles on carbon supports in comparison with oxide supports, which are more common for thermal catalysis. Here, we report the growth morphology and heats of adsorption of Ni vapor deposited onto graphene/Ni(111) at 300 K and 100 K using metal vapor single-crystal adsorption calorimetry and He + low-energy ion scattering (LEIS). These results provide the Ni chemical potential versus particle size, and the Ni/graphene adhesion energy. LEIS intensities suggest that Ni grows as flat-topped face-centered cubic islands with a nearly constant thickness of ~1.5 nm when deposited at 300 K. At 100 K, Ni grows as smaller nanoparticles, well modeled as hemispherical hexagonal close-packed nanoparticles with a density of ~2 × 10 16 particles/m 2 . The Ni chemical potential as a function of average particle diameter in the 0.5 to 4 nm range at 100 K was determined from the heats of Ni gas adsorption. Further, by fitting the measured chemical potential as a function of diameter, we determined an adhesion energy of 3.6 J/m 2 for large Ni particles on graphene/Ni(111). This adhesion energy is in good agreement with previous scanning tunneling microscopy and density functional theory investigations of Ni/graphene/Ni(111).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Atomically Precise Single Metal Oxide Cluster Catalyst with Oxygen–Controlled Activity

Single cluster catalysts (SCCs) consisting of atomically precise metal nanoclusters dispersed on supports represent a new frontier of heterogeneous catalysis. However, the ability to synthesize SCCs with high loading and to precisely introduce non-metal atoms to further tune their catalytic activity and reaction scope of SCCs have been longstanding challenges. In this work, a new interface confinement strategy is developed for the synthesis of a high density of atomically precise Ru oxide nanoclusters (Ru 3 O 2 ) on reduced graphene oxide (rGO), attributed to the suppression of diffusion-induced metal cluster aggregation. Ru 3 O 2 /rGO exhibits a significantly enhanced activity for oxidative dehydrogenation of 1,2,3,4-tetrahydroquinoline (THQ) to quinoline with a high yield (≈86%) and selectivity (≈99%), superior to Ru and RuO 2 nanoparticles, and homogeneous single/multiple-site Ru catalysts. In addition, Ru 3 O 2 /rGO is also capable of efficiently catalyzing more complex oxidative reactions involving three reactants. The theoretical calculations reveal that the presence of two oxygen atoms in the Ru 3 O 2 motif not only leads to a weak hydrogen bonding interaction between the THQ reactant and the active site, but also dramatically depletes the density of states near the Fermi level, which is attributed to the increased positive valence state of Ru and the enhanced oxidative activity of the Ru 3 O 2 cluster for hydrogen abstraction.

36 MATERIALS SCIENCE↗

Nonenzymatic synthesis of RNA and DNA oligomers on hexitol nucleic acid templates: the importance of the A structure

Hexitol nucleic acid (HNA) is an analogue of DNA containing the standard nucleoside bases, but with a phosphorylated 1,5-anhydrohexitol backbone. HNA oligomers form duplexes having the nucleic acid A structure with complementary DNA or RNA oligomers. The HNA decacytidylate oligomer is an efficient template for the oligomerization of the 5'-phosphoroimidazolides of guanosine or deoxyguanosine. Comparison of the oligomerization efficiencies on HNA, RNA, and DNA decacytidylate templates under various conditions suggests strongly that only nucleic acid double helices with the A structure support efficient template-directed synthesis when 5'-phosphoroimidazolides of nucleosides are used as substrates.

Non-NASA Center↗

Yttrium-based Double Perovskite Nanorods for Electrocatalysis

In this work, we investigate the effect of chemical composition of double perovskite nanorods on their versatile electrocatalytic activity not only as supports for the oxidation of small organic molecules but also as catalysts for the oxygen evolution reaction. Specifically, Y 2 CoMnO 6 and Y 2 NiMnO 6 nanorods with average diameters of 300 nm were prepared by a two-step hydrothermal method, in which the individual effects of synthetic parameters, such as the pH, annealing temperature, and precursor ratios on both the composition and morphology, were systematically investigated. When used as supports for Pt nanoparticles, Y 2 CoMnO 6 /Pt catalysts exhibited an electrocatalytic activity for the methanol oxidation reaction, which is 2.1 and 1.3 times higher than that measured for commercial Pt/C and Y 2 NiMnO 6 /Pt. Similarly, the Co-based catalyst support material displayed an ethanol oxidation activity, which is 2.3 times higher than both Pt/C and Y 2 NiMnO 6 /Pt. This clear enhancement in the activity for Y 2 CoMnO 6 can largely be attributed to strong metal-support interactions, as evidenced by a downshift in the binding energy of the Pt 4f bands, measured by XPS, which is often correlated not only with a downshift in the d-band center but also to a decreased adsorption of poisoning adsorbates. Moreover, when used as catalysts for the oxygen evolution reaction, Y 2 CoMnO 6 displayed a much greater activity as compared with Y 2 NiMnO 6 . This behavior can largely be attributed not only to a preponderance of comparatively more favorable oxidation states and electronic configurations but also to the formation of an active layer on the surface of the Y 2 CoMnO 6 catalyst, which collectively give rise to improved performance metrics and greater stability as compared with both IrO 2 and Y 2 NiMnO 6 . Overall, these results highlight the importance of both the chemical composition and the electronic structure of double perovskites, especially when utilized in multi-functional roles as either supports or catalysts.

30 DIRECT ENERGY CONVERSION↗