Liquid-Phase Dehydration of Glycerol to Acrolein with ZSM-5-Based Catalysts in the Presence of a Dispersing Agent.

Liquid-phase dehydration of glycerol to acrolein was investigated with solid acid catalysts, including H-ZSM-5, H3PO4-modified H-ZSM-5, H3PW12O40·14H2O and Cs2.5H0.5PW12O40, in the presence of sulfolane ((CH2)4SO2) as a dispersing agent under atmospheric pressure N2 in a batch reactor. High weak-acidity H-ZSM-5, high temperatures and high-boiling-point sulfolane improved the activity and selectivity for the production of acrolein through suppressing the formation of polymers and coke and promoting the diffusion of glycerol and products. Brønsted acid sites were soundly demonstrated to be responsible for dehydration of glycerol to acrolein by infrared spectroscopy of pyridine adsorption. Brønsted weak acid sites favored the selectivity to acrolein. Combined catalytic and temperature-programmed desorption of ammonia studies revealed that the selectivity to acrolein increased as the weak-acidity increased over the ZSM-5-based catalysts. The ZSM-5-based catalysts produced a higher selectivity to acrolein, while the heteropolyacids resulted in a higher selectivity to polymers and coke.

Stable catalysis of neutral silica-supported potassium lactate for vapour-phase dehydration of lactic acid to acrylic acid - critical role of the support.

We have deeply investigated KNO3-derived silica-supported potassium lactate catalysts for the vapour-phase dehydration of lactic acid (LA) to acrylic acid (AA) by catalytic testing, IR spectroscopic monitoring, ammonia temperature-programmed desorption, isopropyl amine temperature-programmed desorption, IR spectroscopy of pyridine adsorption and thermogravimetric analysis (TGA). A combination of catalytic and acid property studies illustrates that the acidic KNO3/silica systems are not favourable for catalytic selectivity and stability for the production of AA whereas the neutral KNO3/silica systems favour catalytic selectivity and stability for the production of AA. A combination of catalytic and TGA studies indicates that the interaction between KNO3 and silica has a strong promotional effect on catalytic stability for the production of AA. A combination of IR monitoring and catalytic studies suggests that the effects of the surface acidity and the interactions between the potassium salt or base and silica on the catalytic performance are associated with the content and stability of potassium lactate as the catalytic active species. The catalyst stabilization and deactivation under LA dehydration conditions are discussed in detail. The neutral KNO3/silica systems enable the formation of potassium lactate to become dominant whereas the unsupported KNO3 and acidic KNO3/silica systems lead to the formation of poly(potassium acrylate), i.e. catalyst deactivation. This contribution includes for the first time that the dehydration of LA to AA proceeds smoothly with a neutral heterogeneous catalyst.

Pivotal role of reversible NiO6 geometric conversion in oxygen evolution.

Realizing an efficient electron transfer process in the oxygen evolution reaction by modifying the electronic states around the Fermi level is crucial in developing high-performing and robust electrocatalysts1-3. Typically, electron transfer proceeds solely through either a metal redox chemistry (an adsorbate evolution mechanism (AEM), with metal bands around the Fermi level) or an oxygen redox chemistry (a lattice oxygen oxidation mechanism (LOM), with oxygen bands around the Fermi level), without the concurrent occurrence of both metal and oxygen redox chemistries in the same electron transfer pathway1-15. Here we report an electron transfer mechanism that involves a switchable metal and oxygen redox chemistry in nickel-oxyhydroxide-based materials with light as the trigger. In contrast to the traditional AEM and LOM, the proposed light-triggered coupled oxygen evolution mechanism requires the unit cell to undergo reversible geometric conversion between octahedron (NiO6) and square planar (NiO4) to achieve electronic states (around the Fermi level) with alternative metal and oxygen characters throughout the oxygen evolution process. Utilizing this electron transfer pathway can bypass the potential limiting steps, that is, oxygen-oxygen bonding in AEM and deprotonation in LOM1-5,8. As a result, the electrocatalysts that operate through this route show superior activity compared with previously reported electrocatalysts. Thus, it is expected that the proposed light-triggered coupled oxygen evolution mechanism adds a layer of understanding to the oxygen evolution research scene.

Strong Metal-Support Interaction for 2D Materials: Application in Noble Metal/TiB2 Heterointerfaces and their Enhanced Catalytic Performance for Formic Acid Dehydrogenation.

Strong metal-support interaction (SMSI) is a phenomenon commonly observed on heterogeneous catalysts. Here, direct evidence of SMSI between noble metal and 2D TiB2 supports is reported. The temperature-induced TiB2 overlayers encapsulate the metal nanoparticles, resulting in core-shell nanostructures that are sintering-resistant with metal loadings as high as 12.0 wt%. The TiOx -terminated TiB2 surfaces are the active sites catalyzing the dehydrogenation of formic acid at room temperature. In contrast to the trade-off between stability and activity in conventional SMSI, TiB2 -based SMSI promotes catalytic activity and stability simultaneously. By optimizing the thickness and coverage of the overlayer, the Pt/TiB2 catalyst displays an outstanding hydrogen productivity of 13.8 mmol g-1 cat h-1 in 10.0 m aqueous solution without any additive or pH adjustment, with >99.9% selectivity toward CO2 and H2 . Theoretical studies suggest that the TiB2 overlayers are stabilized on different transition metals through an interplay between covalent and electrostatic interactions. Furthermore, the computationally determined trends in metal-TiB2 interactions are fully consistent with the experimental observations regarding the extent of SMSI on different transition metals. The present research introduces a new means to create thermally stable and catalytically active metal/support interfaces for scalable chemical and energy applications.

Materializing efficient methanol oxidation via electron delocalization in nickel hydroxide nanoribbon.

Achieving a functional and durable non-platinum group metal-based methanol oxidation catalyst is critical for a cost-effective direct methanol fuel cell. While Ni(OH)2 has been widely studied as methanol oxidation catalyst, the initial process of oxidizing Ni(OH)2 to NiOOH requires a high potential of 1.35 V vs. RHE. Such potential would be impractical since the theoretical potential of the cathodic oxygen reduction reaction is at 1.23 V. Here we show that a four-coordinated nickel atom is able to form charge-transfer orbitals through delocalization of electrons near the Fermi energy level. As such, our previously reported periodically arranged four-six-coordinated nickel hydroxide nanoribbon structure (NR-Ni(OH)2) is able to show remarkable methanol oxidation activity with an onset potential of 0.55 V vs. RHE and suggests the operability in direct methanol fuel cell configuration. Thus, this strategy offers a gateway towards the development of high performance and durable non-platinum direct methanol fuel cell.

Synthesis of Mesoporous Copper Aluminosilicate Hollow Spheres for Oxidation Reactions.

Hollow functional metal silicate materials have received the most interest due to their large inner space, permeable and functional shell, lighter density, and better use of material compared to their solid counterparts. While tremendous success has been made in the synthesis of individual metal silicates with uniform morphology, the synthesis of multiphase hollow silicates has not been explored yet, although their direct applications could be promising. In this study, mesoporous aluminosilicate spheres (MASS) are transformed to submicrometer copper aluminosilicate hollow spheres (CASHS) via a one-pot hydrothermal process. CASHS has a hollow interior with Cu-Al-Si thorn-like moieties in a lamellar structure on its outer shell. The structure and morphology of CASHS are unique and different from the previously reported tubular copper silicates that are emanated from Stöber silica spheres. Herein, we also demonstrate that the extent of hollowing in CASHS can be attained by controlling the aluminum content of pristine MASS, highlighting the existence of parameters for in situ controlling the shell thickness of hollow materials. The application of CASHS as a potential heterogeneous catalyst has been directed to important oxidation processes such as olefin oxidation and the advanced oxidation process (AOP). In cyclohexene oxidation, for instance, high selectivity to cyclohex-2-en-1-one is achieved under moderate conditions using tert-butyl hydroperoxide as the oxidant. CASHS is a robust heterogeneous catalyst and recyclable for this reaction. CASHS-derived catalysts also favor AOP and enhance the removal of cationic dyes together with H2O2 through an adsorption-degradation process.

In Situ-Generated Supported Potassium Lactate: Stable Catalysis for Vapor-Phase Dehydration of Lactic Acid to Acrylic Acid.

We have studied unsupported, silica gel- and amorphous silica-alumina-supported catalysts derived from K salts for the vapor-phase dehydration of lactic acid (LA) to acrylic acid (AA). A catalytic study shows that the supported catalysts improve the activity and selectivity for the production of AA and decrease the selectivity for the production of propionic acid (PA). The silica-alumina-supported catalysts remain fairly stable in the catalytic performance during 90 h of reaction. The IR spectroscopic characterization combined with the catalytic study demonstrates that potassium lactate (C3H5KO3) in situ generated from LA and a K salt is an important reaction intermediate for the production of AA and the catalytic stability is associated with the chemical stability of C3H5KO3 and the activity for the regeneration of C3H5KO3 in the catalytic cycle. On silica-alumina, C3H5KO3 is well stabilized and smoothly regenerated during the reaction, leading to the good catalytic stability. This work suggests for the first time that lactate salt acts as the true catalytic active species for the dehydration of LA to AA. We also propose a predominant reaction pathway for the vapor-phase dehydration of LA to AA with K salt catalyst systems.

Identifying the Origin and Contribution of Surface Storage in TiO2 (B) Nanotube Electrode by In Situ Dynamic Valence State Monitoring.

Fundamental insight into the surface charging mechanism of TiO2 (B) nanomaterials is limited due to the complicated nature of lithiation behavior, as well as the limitations of available characterization tools that can directly probe surface charging process. Here, an in situ approach is reported to monitor the dynamic valence state of TiO2 (B) nanotube electrodes, which utilizes in situ X-ray absorption spectroscopy (XAS) to identify the origin and contribution of surface storage. A real-time correlation is elucidated between the rate-dependent electrode performance and dynamic Ti valence-state change. A continuous Ti valence state change is directly observed through the whole charging/discharging process regardless of charging rates, which proves that along with the well-known non-faradaic reaction, the surface charging process also originates from a faradaic reaction. The quantification of these two surface storage contributions at different charging rates is further realized through in situ dynamic valence state monitoring combined with traditional cyclic voltammetry measurement. The methodology reported here can also be applied to other electrode materials for the real-time probing of valence state change during electrochemical reactions, the quantification of the faradaic and non-faradaic reactions, and the eventual elucidation of electrochemical surface charging mechanisms.

Crystal Phase and Architecture Engineering of Lotus-Thalamus-Shaped Pt-Ni Anisotropic Superstructures for Highly Efficient Electrochemical Hydrogen Evolution.

The rational design and synthesis of anisotropic 3D nanostructures with specific composition, morphology, surface structure, and crystal phase is of significant importance for their diverse applications. Here, the synthesis of well-crystalline lotus-thalamus-shaped Pt-Ni anisotropic superstructures (ASs) via a facile one-pot solvothermal method is reported. The Pt-Ni ASs with Pt-rich surface are composed of one Ni-rich "core" with face-centered cubic (fcc) phase, Ni-rich "arms" with hexagonal close-packed phase protruding from the core, and facet-selectively grown Pt-rich "lotus seeds" with fcc phase on the end surfaces of the "arms." Impressively, these unique Pt-Ni ASs exhibit superior electrocatalytic activity and stability toward the hydrogen evolution reaction under alkaline conditions compared to commercial Pt/C and previously reported electrocatalysts. The obtained overpotential is as low as 27.7 mV at current density of 10 mA cm-2 , and the turnover frequency reaches 18.63 H2 s-1 at the overpotential of 50 mV. This work provides a new strategy for the synthesis of highly anisotropic superstructures with a spatial heterogeneity to boost their promising application in catalytic reactions.

A Highly Efficient Oxygen Evolution Catalyst Consisting of Interconnected Nickel-Iron-Layered Double Hydroxide and Carbon Nanodomains.

In this work, a one-pot solution method for direct synthesis of interconnected ultrafine amorphous NiFe-layered double hydroxide (NiFe-LDH) (<5 nm) and nanocarbon using the molecular precursor of metal and carbon sources is presented for the first time. During the solvothermal synthesis of NiFe-LDH, the organic ligand decomposes and transforms to amorphous carbon with graphitic nanodomains by catalytic effect of Fe. The confined growth of both NiFe-LDH and carbon in one single sheet results in fully integrated amorphous NiFe-LDH/C nanohybrid, allowing the harness of the high intrinsic activity of NiFe-LDH due to (i) amorphous and distorted LDH structure, (ii) enhanced active surface area, and (iii) strong coupling between the active phase and carbon. As such, the resultant NiFe-LDH/C exhibits superior activity and stability. Different from postdeposition or electrostatic self-assembly process for the formation of LDH/C composite, this method offers one new opportunity to fabricate high-performance oxygen evolution reaction and possibly other catalysts.

The role of metal-support interaction for CO-free hydrogen from low temperature ethanol steam reforming on Rh-Fe catalysts.

Rh-Fe catalysts supported on Ca-Al2O3, MgO and ZrO2 were evaluated in ethanol steam reforming at 623 K and compared to Rh catalysts on the same supports without iron promotion. The metal-support interaction among the three entities, i.e. Rh ↔ Fe2O3 ← support (ZrO2, MgO and Ca-Al2O3) was investigated using H2-chemisorption, TEM, XPS and in situ techniques such as DRIFTS, temperature-resolved XRD and XAS. As compared to the unpromoted Rh catalysts on the same supports, the CO selectivity is depressed in the presence of iron on Rh/MgO and Rh/Ca-Al2O3, the latter being significantly superior. The role of metal-support interaction for CO-free hydrogen generation was unravelled using a combination of techniques. It was found that the reducibility of iron oxide determines the extent of the strong metal support interaction between Rh and Fe2O3 and the reducibility of iron oxide was affected by the support. On Rh-Fe/Ca-Al2O3, a good balance of the interaction between Rh, Fe2O3 and Ca-Al2O3 prevents strong metal support interaction between Rh and Fe2O3 and thus promotes CO elimination via water-gas-shift reaction on Rh-FexOy sites.

Dehydration of lactic acid to acrylic acid over lanthanum phosphate catalysts: the role of Lewis acid sites.

Lanthanum phosphate (LaP) nano-rods were synthesized using n-butylamine as a shape-directing agent (SDA). The resulting catalysts were applied in the dehydration of lactic acid to acrylic acid. Aiming to understand the nature of the active sites, the chemical and physical properties of LaP materials were studied using a variety of characterization techniques. This study showed that the SDA not only affected the porosity of the LaP materials but also modified the acid-base properties. Clearly, the modification of the acid-base properties played a more critical role in determining the catalytic performance than porosity. An optimized catalytic performance was obtained on the LaP catalyst with a higher concentration of Lewis acid sites. Basic sites showed negative effects on the stability of the catalysts. Good stability was achieved when the catalyst was prepared using the appropriate SDA/La ratio.

Biomass Oxidation: Formyl C-H Bond Activation by the Surface Lattice Oxygen of Regenerative CuO Nanoleaves.

An integrated experimental and computational investigation reveals that surface lattice oxygen of copper oxide (CuO) nanoleaves activates the formyl C-H bond in glucose and incorporates itself into the glucose molecule to oxidize it to gluconic acid. The reduced CuO catalyst regains its structure, morphology, and activity upon reoxidation. The activity of lattice oxygen is shown to be superior to that of the chemisorbed oxygen on the metal surface and the hydrogen abstraction ability of the catalyst is correlated with the adsorption energy. Based on the present investigation, it is suggested that surface lattice oxygen is critical for the oxidation of glucose to gluconic acid, without further breaking down the glucose molecule into smaller fragments, because of C-C cleavage. Using CuO nanoleaves as catalyst, an excellent yield of gluconic acid is also obtained for the direct oxidation of cellobiose and polymeric cellulose, as biomass substrates.

XAFCA: a new XAFS beamline for catalysis research.

A new X-ray absorption fine-structure (XAFS) spectroscopy beamline for fundamental and applied catalysis research, called XAFCA, has been built by the Institute of Chemical and Engineering Sciences, and the Singapore Synchrotron Light Source. XAFCA covers the photon energy range from 1.2 to 12.8 keV, making use of two sets of monochromator crystals, an Si (111) crystal for the range from 2.1 to 12.8 keV and a KTiOPO4 crystal [KTP (011)] for the range between 1.2 and 2.8 keV. Experiments can be carried out in the temperature range from 4.2 to 1000 K and pressures up to 30 bar for catalysis research. A safety system has been incorporated, allowing the use of flammable and toxic gases such as H2 and CO.

C-O cleavage of aromatic oxygenates over ruthenium catalysts. A computational study of reactions at step sites.

We studied the C-O cleavage of phenolate and catecholate at step sites of a Ru catalyst using periodic DFT methods at the GGA level. Both C-O scission steps are associated with activation barriers of about 75 kJ mol(-1), hence are significantly more facile than the analogous reactions on Ru terraces. With these computational results, we offer an interpretation of recent experiments on the hydrodeoxygenation of guaiacol (2-methoxyphenol) over Ru/C. We hypothesize that the experimentally observed dependency of the product selectivity on the H2 pressure is related to the availability of step sites on a Ru catalyst.

Predicting adsorption enthalpies on silicalite and HZSM-5: A benchmark study on DFT strategies addressing dispersion interactions.

We evaluated the accuracy of periodic density functional calculations for adsorption enthalpies of water, alkanes, and alcohols in silicalite and HZSM-5 zeolites using a gradient-corrected density functional with empirical dispersion corrections (PBE-D) as well as a nonlocal correlation functional (vdW-DF2). Results of both approaches agree in acceptable fashion with experimental adsorption energies of alcohols in silicalite, but the adsorption energies for n-alkanes in both zeolite models are overestimated, by 21-46 kJ mol(-1). For PBE-D calculations, the adsorption of alkanes is exclusively determined by the empirical dispersion term, while the generalized gradient approximation-DFT part is purely repulsive, preventing the molecule to come too close to the zeolite walls. The vdW-DF2 results are comparable to those of PBE-D calculations, but the latter values are slightly closer to the experiment in most cases. Thus, both computational approaches are unable to reproduce available experimental adsorption energies of alkanes in silicalite and HZSM-5 zeolite with chemical accuracy.

The effect of trivalent cations on the performance of Mg-M-CO(3) layered double hydroxides for high-temperature CO(2) capture.

The effect of trivalent cations on the performance of Mg-M-CO(3) (M=Al, Fe, Ga, Mn) layered double hydroxides (LDHs) for high-temperature CO(2) capture is systematically investigated for the first time. We demonstrate that the M(3+) determines the structure evolution of LDH derivatives under thermal treatment, and finally influences the CO(2) capture capacity. Very different calcination temperatures are required for the different LDHs to obtain their maximum CO(2) capture capacities. To have a clear understanding of the reason behind these big differences the physicochemical properties, thermal stability, and memory effect of the LDHs were investigated. Both the thermal stability and the memory effect of LDHs are greatly influenced by the type of trivalent cation. The CO(2) capture capacities were also evaluated under various conditions. Another important finding of this work is that the quasi-amorphous phase obtained by thermal treatment at the lowest possible temperature gives the highest CO(2) capture capacity.

Skeletal Ru/Cu catalysts prepared from crystalline and quasicrystalline ternary alloy precursors: characterization by X-ray absorption spectroscopy and CO oxidation.

The Ru/Cu system is of historical significance in catalysis. The early development and application of X-ray absorption spectroscopy (XAS) led to the original 'bimetallic cluster" concept for highly-immiscible systems. This work explores alkali leaching of Al-based ternary crystalline and quasicrystalline precursors as a potential route to bulk Ru/Cu alloys. Single-phase ternary alloys at 3 trial compositions; Al(71)Ru(22)Cu(7), Al(70.5)Ru(17)Cu(12.5), and Al(70)Ru(10)Cu(20), were prepared by arc melting of the pure metal components. After leaching, the bimetallic residues were characterized principally by transmission XAS, "as-leached" and after annealing in H(2) (and passivation) in a thermobalance. XRD and BET revealed a nanocrystalline product with a native structure of hexagonal Ru. XPS surface analysis of Ru(22)Cu(7) and Ru(17)Cu(12.5) found only slight enrichment by Cu in the as-leached forms, with little change upon annealing. Ru(10)Cu(20) was highly segregated as-leached. XANES data showed preferential oxidation of Cu in Ru(22)Cu(7), implying that it exists as an encapsulating layer. TG data supports this view since it does not show the distinct two-stage O(2) uptake characteristic of skeletal Ru. Cu K-edge EXAFS data for Ru(22)Cu(7) were unique in showing a high proportion of Ru neighbours. The spacing, d(CuRu) = 2.65 A, was that expected from a hypothetical (ideal) solid solution at this composition, but this is unlikely in such a bulk-immiscible system and Ru K-edge EXAFS failed to confirm bulk alloying. Furthermore its invariance under annealing was more indicative of an interfacial bond between bulk components, although partial alloying with retention of local order cannot entirely be ruled out. The XAS and XPS data were reconciled in a model involving surface and bulk segregation, Cu being present at both the grain exterior and in ultra-fine internal pores. This structure can be considered as the 3-dimensional analogue of the classical type. Preliminary studies in CO and H(2) oxidation were made in a DRIFTS flow reactor with on-line MS, and their activities and selectivities were compared against skeletal Ru and Cu controls, Ru/Al(2)O(3), and Au/Fe(2)O(3). All samples were active in CO oxidation above approximately 50 degrees C, showing light-off temperatures in the range 60-70 degrees C. Ru(22)Cu(7) and Ru(17)Cu(12.5) also showed good selectivities (vs. H(2) oxidation), attributed tentatively to Ru-modified Cu surfaces of varying thickness. These compositions are promising candidates to test in a (PROX) fuel processor to supply purified (CO-free) H(2) to a PEM fuel cell.