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At least 469 records · Page 26

Rapid Synthesis of Rhodium-Palladium Alloy Nanocatalysts

The chemistry of metastable RhPd alloys is not well understood, and well-characterized nanoparticle (NP) examples remain rare. Well-defined and near-monodisperse RhPd NPs were prepared in a simple one-pot approach by using microwave-assisted or conventional heating in reaction times as short as 30 s. The catalytic hydrogenation activity of supported RhPd NP catalysts revealed that short synthesis times resulted in the most-active and most-stable hydrogenation catalysts, whereas longer synthesis times promoted partial Rh-Pd core–shell segregation. Relative to Rh NPs, RhPd NPs resisted deactivation over longer reaction times. Density functional theory (DFT) was employed to estimate the binding energies of H and alkenes on (1 1 1) Rh, Pd, and Rh 0.5 Pd 0.5 surfaces. The DFT results concurred with experiment and concluded that the alkene hydrogenation activity trend was of the order Pd<RhPd<Rh. Rh-to-Pd charge-transfer in the RhPd alloys was found to play an important role in modulating the H binding energy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Probing the Location and Speciation of Elements in Zeolites with Correlated Atom Probe Tomography and Scanning Transmission X-Ray Microscopy

Characterizing materials at nanoscale resolution to provide new insights into structure property performance relationships continues to be a challenging research target due to the inherently low signal from small sample volumes, and is even more difficult for nonconductive materials, such as zeolites. Thus, we present the characterization of a single Cu-exchanged zeolite crystal, namely Cu-SSZ-13, used for NO X reduction in automotive emissions, that was subject to a simulated 135,000-mile aging. By correlating Atom Probe Tomography (APT), a single atom microscopy method, and Scanning Transmission X-ray Microscopy (STXM), which produces high spatial resolution X-ray Absorption Near Edge Spectroscopy (XANES) maps, we show that a spatially non-uniform proportion of the Al was removed from the zeolite framework. Here, the techniques reveal that this degradation is heterogeneous at length scales from micrometers to tens of nanometers, providing complementary insight into the long-term deactivation of this catalyst system.

36 MATERIALS SCIENCE↗

Single-step Conversion of Methyl Ethyl Ketone to Olefins over Zn x Zr y O z Catalysts in Water

In this study we investigated the conversion of aqueous methyl-ethyl-ketone (MEK) to olefin fuel precursors over Zn x Zr y O z mixed oxide catalysts. Experiments were carried out in water as MEK is intended to be produced from the dehydration of 2,3-butanediol in fermentation broth which is highly diluted in water. We demonstrated that Zn x Zr y O z catalysts are highly effective for converting aqueous MEK to C 4 -C 5 olefins. High selectivity to olefins equal to 85% was reached at 92% per pass conversion when under H 2 atmosphere. Catalyst stability was demonstrated for 60 hours' time on stream, highlighting the potential for upgrading 2,3-butanediol contained in fermentation broth without the need for energy-intensive water separation. Increased concentration of MEK in the aqueous feed results in increased activity towards olefin production. However, water inhibits catalyst deactivation from coking. A mechanistic investigation revealed the impact of the reaction environment (inert or reducing atmosphere) on the reaction pathways. In an inert environment, the mechanism involves consecutive aldol condensation of MEK and 3-pentanone intermediate. Under reducing conditions two reaction pathways compete with each other as MEK hydrogenation to butenes occurs concurrently with the aldol condensation/decomposition.

09 BIOMASS FUELS↗

Catalytic Activity of Ti-based MXenes for the Hydrogenation of Furfural

Here, we report on the catalytic activity of Ti-based MXenes (Ti 3 CNT z and Ti 3 C 2 T z ) for biomass transformation. MXenes were found to be active catalysts for the hydrogenation of furfural using either gaseous hydrogen or 2-propanol as solvent and hydrogen source. Both catalysts showed good activity in the conversion of furfural to furfuryl alcohol, with furfuryl ether as the main by-product. Stability tests indicated that Ti 3 CNT z is more stable than Ti 3 C 2 T z against deactivation. Ab initio calculations were used to examine the hydrogenation and etherification reactions pathways and their corresponding reaction energetics on the Ti 3 CNT z MXene. The results indicate that the hydrogenation of the carbonyl bond efficiently proceeds via the heterolytic activation of hydrogen over the metal-oxygen site pair followed by the addition of the proton and hydride to the C and O atoms of the carbonyl. The subsequent hydrogenation of the unsaturated furan ring via metal bound hydrogen, however, is calculated to be much more difficult. Protons bound to the oxygen of the MXene are acidic and can also catalyze the etherification of the resulting alcohols. Finally, the bifunctional acid-metal site pairs also selectively catalyze the hydrogenolysis of the furfuryl alcohol to form 2-methyl furan.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Consequences of Intrapore Liquids on Reactivity, Selectivity, and Stability for Aldol Condensation Reactions on Anatase TiO 2 Catalysts

Abstract This study provides evidence and mechanistic interpretations for the significant consequences of intrapore non‐polar liquids on acetone aldol condensation turnover rates, selectivity to primary dimer products, and catalyst stability for reactions at Lewis acid‐base site pairs on TiO 2 surfaces. These non‐polar liquids confer such benefits through the preferential stabilization of transition states (TS) for adsorption (“entry”) and desorption (“exit”) steps, which place their respective reactants or products within a solvating outer sphere environment. The extent to which non‐polar fluids ( n ‐heptane) form an intrapore liquid phase within TiO 2 voids was obtained from N 2 uptakes using established formalisms that consider the different molal volume, surface tension, and volatility between N 2 and n ‐heptane. Acetone condensation rates are limited by C−H activation, an “entry” step that forms bound prop‐1‐en‐2‐olates via a TS stabilized by intrapore liquids, leading to higher aldol condensation turnover rates as n ‐heptane pressure increases and active TiO 2 surfaces become increasingly immersed within a non‐polar liquid phase. These liquids solvate the late TS structures that mediate the desorption of primary C 6 condensation products even more effectively than those involved in prop‐1‐en‐2‐olate formation or in nucleophilic attack events that later form C−C bonds. Such preferential solvation favors desorption over C−C coupling events, thus disfavoring the formation of larger oligomers that become stranded at active sites, thus leading to much slower deactivation. Moreover, solvation by non‐polar liquids also leads to C 6 alkanones as the sole products formed in a single surface sojourn. These effects of a non‐polar dense phase circumvent the inherent stability, reactivity, and selectivity hurdles that have precluded practical aldol condensation catalysis on Lewis acid‐base pairs at oxide surfaces; these consequences are demonstrated here for TiO 2 catalysts, acetone aldol condensation reactions, and n ‐heptane as the non‐polar liquid but through strategies, concepts, and mechanistic features that extend to other systems. More generally, these observations and their mechanistic origins demonstrate how a contacting liquid preferentially solvates TS structures for elementary steps that involve either reactants arriving from or products entering into an outer sphere environment that contains a dense non‐polar phase.

Kadam, Shashikant A.↗

Effect of Surface Temperature on the Distribution and Reactivity of Rh Active Sites for CO Oxidation

Single–atom catalysts are a fast–emerging area in which late–transition metal atoms are supported on oxides, metals, and carbonaceous supports. They show great promise for selective chemical reactions due to their well–defined active sites, and significantly reduce precious metal loading. However, oxide–supported single–atom catalysts have drawbacks such as deactivation due to sintering, and there are on–going debates about the exact nature of the active sites. Herein we report a model system where the surface temperature during Rh deposition on a copper oxide support dictates the Rh size distribution. Here our temperature–programmed desorption experiments reveal that Rh clusters perform CO oxidation at lower temperature than single atoms, and isotopic labelling demonstrates differences in the mechanism in that the C–O bond is broken and reformed on clusters, as opposed to a pure Mars van Krevelen mechanism for CO oxidation at the single–atom Rh sites. We further examine the cluster size distributions with scanning tunneling microscopy and X–ray photoelectron spectroscopy which confirm the presence of both clusters and single atoms for the lower temperature deposition and only single atoms for the higher temperature deposition. Together, these results provide a fundamental understanding of the differences in the CO oxidation mechanism on Rh atoms and clusters.

36 MATERIALS SCIENCE↗

Impact of Iron Species Dispersion on Fe/ZSM–5 Catalyst Performance for Methane Dehydroaromatization (MDA)

Methane dehydroaromatization (MDA) is one of the most promising technologies for directly transforming methane into aromatics. Unlike the extensively investigated Mo/ZSM-5 catalysts, the structure and, consequently, the catalytic activity of Fe/ZSM-5 are markedly influenced by the method of preparation, as shown here. In this study, we prepared 2 % and 4 % Fe/ZSM-5 catalysts via wet impregnation (WI) and incipient wetness impregnation (IWI). Characterizations (XRD, STEM, UV-Vis, NH 3 -TPD and H 2 -TPR) reveal that 2 %Fe-WI mainly possesses isolated or low-polymerized Fe species within zeolite channels, leading to a rapid activation and a higher benzene yield due to the faster reduction to iron suboxides under MDA conditions. In contrast, 2 %Fe-IWI contains bulk iron oxide aggregates, resulting in a slower activation as these aggregates transform into iron carbide through successive reduction and carbonization. Here, a deactivation kinetic study applied to the 2 % catalysts further demonstrates the quantitative relation between Fe site isolation and catalytic activity. Although both 4 % catalysts inevitably form sizable iron oxide clusters and particles due to the high Fe/Al ratio, similar trends are noted, with the WI catalysts exhibiting a shorter induction/activation period and a higher yield of benzene, paralleling observations made with 2 % catalysts.

03 NATURAL GAS↗

Aerobic Conditions Enhance the Photocatalytic Stability of CdS/CdO x Quantum Dots

Photocatalytic H 2 production through water splitting represents an attractive route to generate a renewable fuel. These systems are typically limited to anaerobic conditions due to the inhibiting effects of O 2 . Here, we report that sacrificial H 2 evolution with CdS quantum dots does not necessarily suffer from O 2 inhibition and can even be stabilised under aerobic conditions. The introduction of O 2 prevents a key inactivation pathway of CdS (over-accumulation of metallic Cd and particle agglomeration) and thereby affords particles with higher stability. These findings represent a possibility to exploit the O 2 reduction reaction to inhibit deactivation, rather than catalysis, offering a strategy to stabilise photocatalysts that suffer from similar degradation reactions.

Chemistry↗

E ‐selective Semi‐hydrogenation of Alkynes under Mild Conditions by a Diruthenium Hydride Complex

Abstract The synthesis, characterization and catalytic activity of a new class of diruthenium hydrido carbonyl complexes bound to the t Bu PNNP expanded pincer ligand is described. Reacting t Bu PNNP with two equiv of RuHCl(PPh 3 ) 3 (CO) at 140 °C produces an insoluble air‐stable complex, which was structurally characterized as [Ru 2 ( t Bu PNNP)H(μ‐H)Cl(μ‐Cl)(CO) 2 ] ( 1 ) using solid‐state NMR, IR and X‐ray absorption spectroscopies and follow‐up reactivity. A reaction with KO t Bu results in deprotonation of a methylene linker to produce [Ru 2 ( t Bu PNNP * )H(μ‐H)(μ‐O t Bu)(CO) 2 ] ( 3 ) featuring a partially dearomatized naphthyridine core. This enables metal‐ligand cooperative activation of H 2 analogous to the mononuclear analogue, [Ru( t Bu PNP*)H(CO)]. In contrast to the mononuclear system, the bimetallic analogue 3 catalyzes the E ‐selective semi‐hydrogenation of alkynes at ambient temperature and atmospheric H 2 pressure with good functional group tolerance. Monitoring the semi‐hydrogenation of diphenylacetylene by 1 H NMR spectroscopy shows the intermediacy of Z ‐stilbene, which is subsequently isomerized to the E ‐isomer. Initial findings into the mode of action of this system are provided, including the spectroscopic characterization of a polyhydride intermediate and the isolation of a deactivated species with a partially hydrogenated naphthyridine backbone.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Precise Control of Dissipative Self-assembly by Light and Electricity

Nature-inspired synthetic dissipative self-assemblies have attracted much attention recently. However, it remains a major challenge to achieve precise control over dissipative supramolecular assembly structures and functions of self-contained systems. Here we combine light and electricity as two clean, and spatiotemporally addressable fuels to provide precise control over the morphology for dissipative self-assembly of a perylene bisimide glycine (PBIg) building block in a self-contained solution. In this design, electrochemical oxidation provides the positive fuel to activate PBIg self-assembly while photoreduction supplies the negative fuel to deactivate the system for disassembly. Further, through programming the two counteracting fuels, we demonstrated the control of PBIg self-assembly into a variety of assembly morphologies in a self-contained system. In addition, by exerting light and electrical dual fuels simultaneously, we could create an active homeostasis exhibiting dynamic instability, leading to morphological change to asymmetric assemblies with curvatures. Such precise control over self-assembly of self-contained systems may find future applications in programming complex active materials as well as formulating pharmaceutical reagents with desired morphologies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Naphthodithiophene‐Fused Porphyrins: Synthesis, Characterization, and Impact of Extended Conjugation on Aromaticity

The fusion of tetrapyrroles with aromatic heterocycles constitutes a useful tool for manipulating their opto-electronic properties. In this work, the synthesis of naphthodithiophene-fused porphyrins was achieved through a Heck reaction-based cascade of steps followed by the Scholl reaction. The naphthodithiophene-fused porphyrins display a unique set of optical and electronic properties. Fusion of the naphtho[2,1-b:3,4-b’]dithiophene to porphyrin (F2VTP) leads to a ~20% increase in the fluorescence lifetime, which is accompanied, unexpectedly, by a more than two-fold drop in the emission quantum yield (ϕ=0.018). In contrast, fusion of the isomeric naphtho[1,2-b:4,3-b’]dithiophene to porphyrin (F3VPT) results in a ~1.5-fold increase in the fluorescence quantum yield (ϕ=0.13) with a concomitant ~30 % increase in the fluorescence lifetime. This behavior suggests that fusion of the porphyrin with the naphthodithiopheno-system mainly affects the radiative rate constant in the Q-state deactivation pathway, where the effects of the isomeric naphtho[2,1-b:3,4-b’]dithiophene- versus naphtho[1,2-b:4,3-b’]dithiophene-fusion are essentially the opposite. Interestingly, nucleus-independent chemical shifts analysis revealed a considerable difference between the aromaticities of these two isomeric systems. Furthermore, our results demonstrate that subtle structural differences in the fused components of the porphyrin can be reflected in rather significant differences between the photophysical properties of the resulting systems.

Chemistry↗

Micro‐ and Nanoscale Heterogeneities in Zeolite Beta as Measured by Atom Probe Tomography and Confocal Fluorescence Microscopy

Micro- and nanoscale information on the activating and deactivating coking behaviour of zeolite catalyst materials increases our current understanding of many industrially applied processes, such as the methanol-to-hydrocarbon (MTH) reaction. Atom probe tomography (APT) was used to reveal the link between framework and coke elemental distributions in 3D with sub-nanometre resolution. APT revealed 10–20 nanometre-sized Al-rich regions and short-range ordering (within nanometres) between Al atoms. With confocal fluorescence microscopy, it was found that the morphology of the zeolite crystal as well as the secondary mesoporous structures have a great effect on the microscale coke distribution throughout individual zeolite crystals over time. Additionally, a nanoscale heterogeneous distribution of carbon as residue from the MTH reaction was determined with carbon-rich areas of tens of nanometres within the zeolite crystals. Finally, a short length-scale affinity between C and Al atoms, as revealed by APT, indicates the formation of carbon-containing molecules next to the acidic sites in the zeolite.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hydrogen Peroxide‐Induced Overoxidation of Fe−N−C Catalysts: Implications for ORR Activity

Fe−N−C (iron-nitrogen-carbon) electrocatalysts have emerged as promising alternatives to precious metals for the oxygen reduction reaction (ORR), but they remain insufficiently stable for widespread adoption in fuel cell technologies. One plausible mechanism to explain this lack of stability, and the associated catalyst degradation, is oxidative attack on the catalyst surface by hydrogen peroxide, a non-selective byproduct of the ORR. In this work, we perform a detailed analysis of this degradation mechanism, using a combination of periodic Density Functional Theory (DFT) calculations and ab-initio molecular dynamics (AIMD) simulations to probe the thermodynamics and kinetics of hydrogen peroxide activation on a series of candidate active sites for the Fe−N−C catalyst. The results demonstrate that carbon atoms neighbouring FeN 4 active sites can be strongly over-oxidized via formation of hydroxyl or epoxy groups when hydrogen peroxide is present in the electrolyte. In most cases, the interaction between the over-oxidizing groups and the ORR reaction intermediates reduces the ORR activity, and we further propose that the over-oxidized sites are likely precursors to irreversible carbon corrosion and further catalyst deactivation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Acid-Functionalized Mesoporous Carbon: An Efficient Support for Ruthenium-Catalyzed γ-Valerolactone Production

The hydrogenation of levulinic acid has been studied using Ru supported on ordered mesoporous carbons (OMCs) prepared by soft-templating. P- and S-containing acid groups were introduced by postsynthetic functionalization before the addition of 1% Ru by incipient wetness impregnation. These functionalities and the reaction conditions mediate the activity and selectivity of the levulinic acid hydrogenation. The presence of Scontaining groups (Ru/OMC-S and Ru/OMC-P/S) deactivates the Ru catalysts strongly, whereas the presence of P-containing groups (Ru/OMC-P) enhances the activity compared to that of pristine Ru/OMC. Under mild conditions (70 8C and 7 bar H2) the catalyst shows high selectivity to g-valerolactone (GVL; >95%) and high stability on recycling. However, under more severe conditions (200 8C and pH2=40 bar) Ru/OMC-P is particularly able to promote GVL ring-opening and the consecutive hydrogenation to pentanoic acid.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Recent Progress in Electrochemical Nitrogen Reduction on Transition Metal Nitrides

Distributed electrochemical nitrogen reduction reaction (ENRR) powered by renewable energy for the on-site production of ammonia is an attractive alternative to the industrial Haber–Bosch process, which is responsible for roughly 2 % of global energy consumption. Here, in this Review, we summarize recent progress in the ENRR catalyzed by transition metal nitrides (TMNs). The unique electronic structures of TMNs make them promising ENRR catalysts for active and selective ammonia production, which have been predicted theoretically and demonstrated experimentally. Reaction pathways and deactivation mechanisms of the ENRR on different TMNs are surveyed, and current understanding of structure-activity relations is discussed. To develop highly active, selective, and stable TMN catalysts for industrial-scale ENRR, membrane electrode assembly configuration is recommended in catalyst evaluation. Furthermore, we highlight the importance of developing mechanistic understanding on ENRR with different operando spectroscopic techniques.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hydrogenolysis of Poly(Ethylene–co–Vinyl Alcohol) and Related Polymer Blends over Ruthenium Heterogeneous Catalysts

The hydrogenolysis of polymers is emerging as a promising approach to deconstruct plastic waste into valuable chemicals. Yet, the complexity of plastic waste, including multilayer packaging, is a significant barrier to handling realistic waste streams. Herein, we reveal fundamental insights into a new chemical route for transforming a previously unaddressed fraction of plastic waste – poly(ethylene–co­­–vinyl alcohol) (EVOH) and related polymer blends – into alkane products. Additionally, we report that Ru/ZrO2 is active for the concurrent hydrogenolysis, hydrogenation, and hydrodeoxygenation of EVOH and its thermal degradation products into alkanes (C1–C35) and water. Detailed reaction data, product analysis, and catalyst characterization reveal that the in–situ thermal degradation of EVOH forms aromatic intermediates that are detrimental to catalytic activity. Increased hydrogen pressure promotes hydrogenation of these aromatics, preventing catalyst deactivation and improving alkane product yields. Calculated apparent rates of C–C scission reveal that the hydrogenolysis of EVOH is slower than low–density polyethylene. We apply these findings to achieve hydrogenolysis of EVOH/polyethylene blends and elucidate the sensitivity of hydrogenolysis catalysts to such blends. Overall, we demonstrate progress towards efficient catalytic processes for the hydroconversion of waste multilayer film plastic packaging into valuable products.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Active and Stable PtPd Diesel Oxidation Catalysts under Industry‐Defined Test Protocols

Nanoparticle-supported Pt and Pd catalysts are employed industrially to convert CO and hydrocarbon residue from incomplete diesel fuel combustion into more environmentally-benign products. However, these catalysts deactivate over time due to sintering, especially for Pt nanoparticles which readily generate volatile species under high operating temperatures. Here, we turned the detrimental vapor-mediated sintering of Pt into an advantage by using a physical mixture of Pt and Pd catalysts prepared using a raspberry-colloid-templating (RCT) method. The RCT method produced Pt/Al 2 O 3 and Pd/Al 2 O 3 catalysts with partially embedded NPs to inhibit surface-mediated sintering pathways. As validated using an industry-defined emission control test protocol, aging a physical mixture of Pt/Al 2 O 3 and Pd/Al 2 O 3 at high temperature produced an alloyed PtPd/Al 2 O 3 catalyst that outperformed the fresh catalyst mixture and both individual catalysts for hydrocarbon conversion, while exhibiting high catalytic stability and resistance to sintering and to SO 2 poisoning. X-ray photoelectron spectroscopy revealed that in the aged catalyst mixture, half of the Pd content existed in the more active metallic state, compared to the less active oxide forms in the fresh mixture and both individual catalysts, explaining the unusual activity enhancement. Our results represent a practical approach to producing active and stable PtPd/Al 2 O 3 diesel oxidation catalysts for emission control applications.

Lim, Kang Rui Garrick [Harvard University, Cambrid↗

Simultaneous Determination of Halogens and Metals in Waste Plastic Pyrolysis Oil by Inductively Coupled Plasma Mass Spectrometry

A major barrier to integrating pyrolysis-derived oil into conventional refinery technology is the presence of impurities, particularly halogens and metals, that can deactivate catalysts. This study presents a novel, cost-effective approach for the simultaneous analysis of a subset of halogens, metals, nonmetals, and metalloids in complex, industrially relevant distilled pyrolysis oil samples, this was previously achievable only through multiple techniques. Excellent results were obtained using a widely accessible inductively coupled plasma mass spectrometry (ICP-MS) method with helium gas mode and standard laboratory consumables, enabling high-throughput analysis and efficient evaluation of adsorbent performance. Sample preparation is straightforward, requiring only dilution in a compatible matrix, and provides accurate and precise quantification, with 75%–137% spike recovery for Be, Ti, V, Cr, Fe, Ni, Co, Cu, As, Se, Mo, Cd, Sb, Tl, and Pb, and 62%–65% spike recovery for Cl and 109%–133% spike recovery for Br. Additionally, an enhanced version of the method using ICP-MS/MS and hydrogen gas is described, which has higher accuracy with 69%–112% spike recovery for Be, B, Ti, V, Fe, Co, Ni, Cu, As, Se, Mo, Cd, Sb, Tl, and Pb, with 85%–102% spike recovery for Cl and 63%–93% spike recovery for Br. Helium mode detection limits for industrially relevant elements (V, Fe, Ni, Cu, As, and Pb) are less than 1.7 µg/kg, and less than 0.2 mg/kg for Br and Cl. Furthermore, this methodology facilitates rapid systematic evaluation of adsorption capacities of materials under time-on-stream conditions and supports robust comparisons across diverse operating environments.

Lazarcik, James [University of Wisconsin-Madison, ↗