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Transforming polyolefin waste into liquid alkanes through tandem cracking‐alkylation reactions catalyzed by Lewis‐acid chlorides offers an efficient route for single‐step plastic upcycling. Lewis acids in dichloromethane establish a polar environment that stabilizes carbenium ion intermediates and catalyzes hydride transfer, enabling breaking of polyethylene C−C bonds and forming C−C bonds in alkylation. Here, we show that efficient and selective deconstruction of low‐density polyethylene (LDPE) to liquid alkanes is achieved with anhydrous aluminum chloride (AlCl3) and gallium chloride (GaCl3). Already at 60 °C, complete LDPE conversion was achieved, while maintaining the selectivity for gasoline‐range liquid alkanes over 70 %. AlCl3 showed an exceptional conversion rate of 5000 gLDPEmolcat-1h-1 ${{{\rm g}}_{{\rm L}{\rm D}{\rm P}{\rm E}}{{\rm \ }{\rm m}{\rm o}{\rm l}}_{{\rm c}{\rm a}{\rm t}}^{-1}{{\rm \ }{\rm h}}^{-1}}$ , surpassing other Lewis acid catalysts by two orders of magnitude. Through kinetic and mechanistic studies, we show that the rates of LDPE conversion do not correlate directly with the intrinsic strength of the Lewis acids or steric constraints that may limit the polymer to access the Lewis acid sites. Instead, the rates for the tandem processes of cracking and alkylation are primarily governed by the rates of initiation of carbenium ions and the subsequent intermolecular hydride transfer. Both jointly control the relative rates of cracking and alkylation, thereby determining the overall conversion and selectivity. [ABSTRACT FROM AUTHOR]

Understanding the adsorption and reactivity of carboxylic acids on oxide surfaces is of great interest in catalysis for biomass upgrading via ketonization, a carbon–carbon coupling reaction. Herein, we investigate the adsorption and reaction of acetic acid on anatase TiO2(101) using scanning tunneling microscopy, infrared spectroscopy, temperature programmed reaction, and density functional theory calculations. We demonstrate the adsorption of acetic acid can form two intermediates: (1) dissociated, bidentate acetate with an associated bridging hydroxyl, and (2) molecular, monodentate acetic acid. The coexistence of ordered phases with increasing monolayer (ML) saturation coverages consisting of (1) pure acetate (0.5 ML), (2) mixed acetate/acetic acid (0.67 ML), (3) mixed acetate/acetic acid (1.0 ML) and (4) pure acetic acid demonstrates similar energetics for both acetate and acetic acid species. Under ultra-high vacuum conditions, the presence of both monodentate acetic acid and bidentate acetate was observed below room temperature, while solely bidentate acetate was observed up to 575 K. The deprotonation of acetic acid produces water at 280 K, while the thermal decomposition of bidentate acetate produces ketene and acetic acid at 645 K. This model study provides detailed insight into the stability and reactivity of carboxylic acid surface-bound intermediates, which could participate during ketonization reactions for biomass upgrading. [ABSTRACT FROM AUTHOR]

In catalysis, MgO is often used to modify the acid–base properties of support oxides and to stabilize supported metal atoms and particles on oxides. In this study, we show how the sublimation of MgO powder can be used to deposit MgO monomers, hither on anatase TiO2(101). A combination of x-ray electron spectroscopy, high-resolution scanning tunneling microscopy, and density functional theory is employed to gain insight into the MgO monomer binding, electronic and vibrational properties, and thermal stability. In the most stable configuration, the Mg and O of the MgO monomer bind to two surface oxygens and one undercoordinated surface titanium, respectively. The additional binding weakens the Mg–O monomer bond and makes Mg more ionic. The monomers are thermally stable up to 600 K, where the onset of diffusion into the TiO2 bulk is observed. The monomeric MgO species on TiO2(101) represent an ideal atomically precise system with modified acid–base properties and will be employed in our future catalytic studies. [ABSTRACT FROM AUTHOR]

Supported single-atom catalysts (SACs) have gained increasing attention for improved catalytic activity and selectivity for industrially relevant reactions. In this study, we explore the hydrogenation of acetylene over single Pt, Ru, Rh, Pd, and Ir atoms supported on the Fe3O4(001) surface using density functional theory calculations. The thermodynamic profile of H diffusion is significantly modified by the type of single metal atoms used, suggesting that H spillover from the single atom dopant to the Fe3O4(001) surface is favored and will likely lead to high H coverages of the functioning catalyst. Correspondingly, as the surface H coverage increases, the important desorption step of ethylene becomes energetically competitive against the detrimental hydrogenation steps of ethylene to ethane. A kinetic model is employed to explore how the activity and selectivity of SACs toward ethylene production change as a function of mass of the catalyst loaded into a flow reactor. Overall, we show that the selectivity of SACs toward ethylene production can be tuned by considering the proper type of metal and controlling the redox state of the support. [ABSTRACT FROM AUTHOR]

Electrocatalytic hydrogenation (ECH) of biomass-derived feedstocks has a critical dependence on the molecular structure of the organic and its adsorption on the electrode surface. In this study, we investigated the role of functional groups in the adsorption of the organic molecule on the charged Pd (111) surface and its subsequent effect on organic reduction in electrochemical hydrogenation of organic molecules. With three aromatic carbonyls of benzaldehyde (BZD), acetophenone (ACE), and vanillin (VAN), we rationalize molecular-scale adsorption and interfacial charge transfer processes by employing density-functional-theory based ab initio molecular dynamics simulations. We observe that the functional group and electrode charge strongly affect the proximity of organic molecule to the Pd (111) surface, where distances of aromatic ring and carbonyl group of the organic on the electrode change distinctively with functional groups and charge state of electrode, which strongly impact reduction of organics on the surface. Calculations of differential electron density show the strongest reduction with benzaldehyde via interfacial electron transfer from the charged Pd surface. We also observe that the interaction between the functional groups and solvent (VAN > BZD > ACE) significantly influence the organic interaction with the charged electrode (BZD > VAN > ACE), resulting in the net interaction energy between the organic and the electrode in the order of BZD > ACE > VAN. Experimental measurement of ECH rate also show the same trend of the net interaction energy. These results demonstrate the significance of solvent effect on the reducibility of organic molecules on electrodes. [Display omitted] • The organic functional group has a large impact on ECH with metal electrode. • The organic functional group influences structure and binding on metal surface. • Solvent also impacts the organic-electrode interaction energy. • The organic having the lowest reduction potential shows the highest ECH rate. [ABSTRACT FROM AUTHOR]

[Display omitted] • A site preference for H 2 adsorption is different between Pt and Pd surfaces. • The site competition between H and benzaldehyde is seen on Pt unlike Pd surface. • The benzaldehyde is strongly adsorbed and hence reduced on the charged Pd surface. • The presence of H 2 O solvent and surface charge impacts hydrogenation on Pd(111). Understanding the hydrogenation of organic compounds in the aqueous phase has always been fundamentally important for improving carbon neutral pathways to fuels and value-added chemicals. In this study, we investigated both thermodynamic and kinetic profiles of benzaldehyde hydrogenation over the Pd(111) and Pt(111) metal surfaces using density functional theory (DFT) and ab initio molecular dynamic (AIMD) simulations. The adsorption of H 2 shows the mixed preference of H adsorption sites on the Pt(111), while the fcc adsorption site is dominant for H on the Pd(111). When benzaldehyde is added to the systems, we observe a strong reduction of benzaldehyde on charged Pd (111) surface compared with that on neutral surface. In contrast, charged state of the Pt(111) surface does not change their interaction. Subsequent hydrogenation reaction of benzaldehyde over Pd(111), proceeding via Langmuir-Hinshelwood mechanism, is affected by two major factors: the presence of H 2 O solvent and surface charge. The presence of H 2 O solvent greatly reduces the activation energy of C H and O H bond formation during the hydrogenation process. Furthermore, the hydrogenation step via C H bond formation is preferred thermodynamically and kinetically over O H bond formation during thermocatalytic hydrogenation, while the opposite trend holds true during electrocatalytic hydrogenation. [ABSTRACT FROM AUTHOR]

The analogy between single‐atom catalysts (SACs) and molecular catalysts predicts that the specific catalytic activity of these systems is constant. We provide evidence that this prediction is not necessarily true. As a case in point, we show that the specific activity over ceria‐supported single Pd atoms linearly increases with metal atom density, originating from the cumulative enhancement of CeO2 reducibility. The long‐range electrostatic footprints (≈1.5 nm) around each Pd site overlap with each other as surface Pd density increases, resulting in an observed deviation from constant specific activity. These cooperative effects exhaust previously active O atoms above a certain Pd density, leading to their permanent removal and a consequent drop in reaction rate. The findings of our combined experimental and computational study show that the specific catalytic activity of reducible oxide‐supported single‐atom catalysts can be tuned by varying the surface density of single metal atoms. [ABSTRACT FROM AUTHOR]

The hydrogenation of benzaldehyde to benzyl alcohol on carbon‐supported metals in water, enabled by an external potential, is markedly promoted by polarization of the functional groups. The presence of polar co‐adsorbates, such as substituted phenols, enhances the hydrogenation rate of the aldehyde by two effects, that is, polarizing the carbonyl group and increasing the probability of forming a transition state for H addition. These two effects enable a hydrogenation route, in which phenol acts as a conduit for proton addition, with a higher rate than the direct proton transfer from hydronium ions. The fast hydrogenation enabled by the presence of phenol and applied potential overcompensates for the decrease in coverage of benzaldehyde caused by competitive adsorption. A higher acid strength of the co‐adsorbate increases the intensity of interactions and the rates of selective carbonyl reduction. [ABSTRACT FROM AUTHOR]

Water-lean CO2 capture solvents show promise for more efficient and cost-effective CO2 capture, although their long-term behavior in operation has yet to be well studied. New observations of extended structure solvent behavior show that some solvent formulations transform into a glass-like phase upon aging at operating temperatures after contact with CO2. The glassification of a solvent would be detrimental to a carbon-capture process due to plugging of infrastructure, introducing a critical need to decipher the underlying principles of this phenomenon to prevent it from happening. We present the first integrated theoretical and experimental study to characterize the nano-structure of metastable and glassy states of an archetypal single-component alkanolguanidine carbon-capture solvent and assess how minute changes in atomic-level interactions convert the solvent between metastable and glass-like states. Small-angle neutron scattering and neutron diffraction coupled with small- and wide-angle X-ray scattering analysis demonstrate that minute structural changes in solution precipitae reversible aggregation of zwitterionic alkylcarbonate clusters in solution. Our findings indicate that our test system, an alkanolguanidine, exhibits a first-order phase transition, similar to a glass transition, at approximately 40 °C—close to the operating absorption temperature for post-combustion CO2 capture processes. We anticipate that these phenomena are not specific to this system, but are present in other classes of colvents as well. We discuss how molecular-level interactions can have vast implications for solvent-based carbon-capture technologies, concluding that fortunately in this case, glassification of water-lean solvents can be avoided as long as the solvent is run above its glass transition temperature. [ABSTRACT FROM AUTHOR]

Acid functionalization of a carbon support allows to enhance the electrocatalytic activity of Pd to hydrogenate benzaldehyde to benzyl alcohol proportional to the concentration of Brønsted‐acid sites. In contrast, the hydrogenation rate is not affected when H2 is used as a reduction equivalent. The different responses to the catalyst properties are shown to be caused by differences in the hydrogenation mechanism between the electrochemical and the H2‐induced hydrogenation pathways. The enhancement of electrocatalytic reduction is realized by the participation of support‐generated hydronium ions in the proximity of the metal particles. [ABSTRACT FROM AUTHOR]

The thermodynamic state of H2 adsorbed on Pt in the aqueous phase was determined by kinetic analysis of H2 reacting with D2O to HDO, HD, and D2, and by DFT‐based ab initio molecular dynamics simulations of H2 adsorption on Pt(111), Pt(110), and Pt nanoparticles. Dissociative adsorption of H2 on Pt is significantly weakened in the aqueous phase compared to adsorption at gas–solid interfaces. Water destabilizes the adsorbed H atoms, decreasing the heat of adsorption by 19–22 kJ molH2-1 while inducing an additional entropy loss of 50–70 J molH2-1  K−1. Upon dissociative adsorption of H2, the average distance of water from the Pt surface increases and the liquid adopts a structure that is more ordered than before close to the Pt surface, which limits the translation mobility of the adsorbed H atoms. The presence of hydrated hydronium ions next to the Pt surface further lowers the H−Pt bond strength. The thermodynamic state of H2 adsorbed on Pt in the aqueous phase was determined via kinetic analysis of H2 reacting with D2O and by DFT‐based ab initio molecular dynamics simulations of H2 adsorption on Pt(111). Compared to the gas–solid interface, the presence of liquid water weakens the dissociative adsorption by decreasing the heat of adsorption and inducing a larger loss of entropy. [ABSTRACT FROM AUTHOR]

Keywords: CO oxidation; electrostatic effects; Pd/CeO2; reducible oxide supports EN CO oxidation electrostatic effects Pd/CeO2 reducible oxide supports 23028 23028 1 10/06/21 20211011 NES 211011 B Just like a well-played pool game b , single atom catalysts lead to novel and exciting catalytic routes. Back Cover: Surface Density Dependent Catalytic Activity of Single Palladium Atoms Supported on Ceria (Angew. CO oxidation, electrostatic effects, Pd/CeO2, reducible oxide supports. [Extracted from the article]

Sung June Cho, Roger Rousseau, Janos Szanyi, Ja Hun Kwak et al. stellen in ihrem Forschungsartikel auf S. 22951 eine kombinierte experimentelle und theoretische Studie vor, die die Rolle von Pd-Einzelatomen auf CeO SB 2 sb und die elektronischen Effekte in der CO-Oxidation beleuchtet. CO oxidation, electrostatic effects, Pd/CeO2, reducible oxide supports Keywords: CO oxidation; electrostatic effects; Pd/CeO2; reducible oxide supports EN CO oxidation electrostatic effects Pd/CeO2 reducible oxide supports 23212 23212 1 10/06/21 20211011 NES 211011 B Wie bei einem Billardspiel b können Einzelatomkatalysatoren zu neuen und aufregenden katalytischen Reaktionspfaden führen. [Extracted from the article]

• We study the electro-reduction of benzaldehyde on Au(111) using multiscale modeling. • Electrode charge density decreases the surface coverage of benzaldehyde on Au(111). • Solvents with alcohols increase the coverage of benzaldehyde on the catalyst. • The Butler-Volmer behavior is recaptured using scanning tunneling microscope theory. • Solvent compositions play a key role in the electro-reduction of organic molecules. We present a multiscale modeling study on the electro-reduction of benzaldehyde (BZY) on Au(111) under realistic electrochemical conditions. To model the electrochemical cell, we adopt a capacitor model in which complex solvents are confined between a Au cathode and a carbon anode. Classical molecular dynamics simulations reveal that electrode charge density and the presence of alcohol show strong effects on the density, adsorption geometry and dynamics of benzaldehyde on the Au electrode. Under charging conditions, the surface concentration of benzaldehyde on the Au electrode decreases, while the content of other species increases. Finally, we proposed a scheme that correlates the electric current running through the Au/solvent interface with the applied bias. This study provides a molecular level understanding of how solvent composition, in this case water/alcohol content, controls the activity of electrocatalytic hydrogenation [ABSTRACT FROM AUTHOR]

Expandable clays such as montmorillonite have interlayer exchange sites whose hydration state can be systematically varied from near anhydrous to almost bulk-like water conditions. This phenomenon has new significance with the simultaneous implementation of geological sequestration and secondary utilization of CO 2 to both mitigate climate warming and enhance extraction of methane from hydrated clay-rich formations. In this study, the partitioning of CO 2 and H 2 O between Na-, Ca-, and Mg-exchanged montmorillonite and variably hydrated supercritical CO 2 (scCO 2 ) was investigated using in situ X-ray diffraction (HXRD), infrared (IR) spectroscopic titrations, and quartz crystal microbalance (QCM) measurements. Density functional theory calculations provided mechanistic insights. Structural volumetric changes were correlated to quantified changes in sorbed H 2 O and CO 2 concentrations as a function of percent H 2 O saturation in scCO 2 . Intercalation of CO 2 is inhibited when the clay is fully collapsed (dehydrated interlayer), peaks sharply with the introduction of some H 2 O and partial expansion of the interlayer region, and then decreases systematically with further hydration of the clay. This behavior is discussed in the context of recent theoretical calculations of the montmorillonite H 2 O–CO 2 system. [ABSTRACT FROM AUTHOR]

In situ Al K-edge X-ray absorption near edge structure (XANES) and Extended X-ray absorption fine structure (EXAFS) spectroscopy in conjunction with ab initio molecular dynamics (AIMD) simulations show that adsorption of 1-propanol alters the structure of the Brønsted acid site through changes in the associated aluminum-oxygen tetrahedron in zeolite H-MFI. The decreasing intensity of the pre-edge signal of the in situ Al K-edge XANES spectra with increasing 1-propanol coverage shows that Al T-sites become more symmetric as the sorbed alcohol molecules form monomers, dimers, and trimers. The adsorption of monomeric 1-propanol on Brønsted acid sites reduces the distortion of the associated Al T-site, shortens the Al-O distance, and causes the formation of a Zundel-like structure. With dimeric and trimeric alcohol clusters, the zeolite proton is fully transferred to the alcohols and the aluminum-oxygen tetrahedron becomes fully symmetric. The subtle changes in Al-K-edge XANES in the presence of sorbate structures, with the use of theory, are used to probe the local zeolite structures and provide a basis to predict the population and chemical state of the sorbed species., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)