Effect of the reductive treatment on the state and electrocatalytic behavior of Pt in catalysts supported on Ti0.8Mo0.2O2-C composite

Ti(1-x)MoxO2-carbon composites are promising new supports for Pt-based electrocatalysts in polymer electrolyte membrane fuel cells offering exciting catalytic properties and enhanced stability against electrocorrosion. Pt and the mixed oxide form a couple liable for strong metal-support interaction (SMSI) phenomenon, generally manifesting itself in decoration of the metal particles by ultrathin layers of the support material upon annealing under reductive conditions. The aim of this work is to evaluate the SMSI phenomenon as a potential strategy for tailoring the properties of the electrocatalyst. A 20 wt% Pt/50 wt% Ti0.8Mo0.2O2-50 wt% C electrocatalyst prepared on Black Pearls 2000 carbon functionalized with HNO3 and glucose was reduced at 250 °C in H2 in order to induce SMSI. The electrocatalytic properties and the stability of the reduced and the original catalysts were analyzed by cyclic voltammetry and COads stripping voltammetry. Structural investigations as well as X-ray photoelectron spectroscopy (XPS) measurements were performed in order to obtain information about the details of the interaction between the oxide and the Pt particles. The electrochemical experiments pointed out a small loss of the electrochemically active surface area of Pt in the reduced catalyst along with enhanced stability with respect to the original one, while structural studies suggested only a minimal decrease of the Pt dispersion. At the same time, hydrogen exposure experiments combined with XPS demonstrated the presence of Mo species directly adsorbed on the Pt surface. Thus, the properties of the reduced catalyst can be traced to decoration of the surface of Pt by Mo-containing species.

Applicability of Nickel-Based Catalytic Systems for Hydrodehalogenation of Recalcitrant Halogenated Aromatic Compounds

This review summarizes recent applications of nickel as a nonprecious metal catalyst in hydrodehalogenation (HDH) reactions of halogenated aromatic compounds (Ar–Xs). Nickel-based HDH catalysts were developed for reductive treatment of both waste containing concentrated Ar–Xs (mainly polychlorinated benzenes) and for wastewater contaminated with Ar–Xs. Ni-catalyzed HDH enables the production of corresponding nonhalogenated aromatic products (Ar–Hs), which are principally further applicable/recyclable and/or Ar–Hs, which are much more biodegradable and can be mineralized during aerobic wastewater treatment. Developed HDH methods enable the utilization of both gaseous hydrogen via the direct HDH process or other chemical reductants as a source of hydrogen utilized in the transfer of the hydrodehalogenation process. This review highlights recent and major developments in Ni-catalyzed hydrodehalogenation topic since 1990.

In situ formation of ZnOx species for efficient propane dehydrogenation

Propane dehydrogenation (PDH) to propene is an important alternative to oil-based cracking processes, to produce this industrially important platform chemical1,2. The commercial PDH technologies utilizing Cr-containing (refs. 3,4) or Pt-containing (refs. 5–8) catalysts suffer from the toxicity of Cr(vi) compounds or the need to use ecologically harmful chlorine for catalyst regeneration9. Here, we introduce a method for preparation of environmentally compatible supported catalysts based on commercial ZnO. This metal oxide and a support (zeolite or common metal oxide) are used as a physical mixture or in the form of two layers with ZnO as the upstream layer. Supported ZnOx species are in situ formed through a reaction of support OH groups with Zn atoms generated from ZnO upon reductive treatment above 550 °C. Using different complementary characterization methods, we identify the decisive role of defective OH groups for the formation of active ZnOx species. For benchmarking purposes, the developed ZnO–silicalite-1 and an analogue of commercial K–CrOx/Al2O3 were tested in the same setup under industrially relevant conditions at close propane conversion over about 400 h on propane stream. The developed catalyst reveals about three times higher propene productivity at similar propene selectivity.

The Impact of Biomass and Acid Loading on Methanolysis during Two-Step Lignin-First Processing of Birchwood

We optimized the solvolysis step in methanol for two-step lignin-first upgrading of woody biomass. Birchwood was first converted via sulfuric acid methanolysis to cellulose pulp and a lignin oil intermediate, which comprises a mixture of lignin oligomers and C5 sugars in the methanol solvent. The impact of reaction temperature (140–200 °C), acid loading (0.24–0.81 wt%, dry biomass), methanol/biomass ratio (2.3/1–15.8/1 w/w) and reaction time (2 h and 0.5 h) was investigated. At high biomass loadings (ratio < 6.3/1 w/w), operation at elevated pressure facilitates delignification by keeping methanol in the liquid phase. A high degree of delignification goes together to a large extent with C5 sugar release, mostly in the form of methyl xylosides. Gel permeation chromatography and heteronuclear single quantum coherence NMR of lignin fractions obtained at high acid (0.81 wt%) and low biomass (15.8/1 w/w) loading revealed extensive cleavage of β-O-4′ bonds during acidolysis at 180 °C for 2 h. At an optimized methanol/biomass ratio of 2.3/1 w/w and acid loading (0.24 wt%), more β-O-4′ bonds could be preserved, i.e., about 33% after 2 h and 47% after 0.5 h. The high reactivity of the extracted lignin fragments was confirmed by a second hydrogenolysis step. Reductive treatment with Pd/C under mild conditions led to disappearance of ether linkages and molecular weight reduction in the hydrotreated lignin oil.

Synthesis of dibenzosuberenone-based novel polycyclic π-conjugated dihydropyridazines, pyridazines and pyrroles

The synthesis of novel polycyclic π-conjugated dihydropyridazines, pyridazines, and pyrroles was studied. Dihydropyridazine dyes were synthesized by inverse electron-demand Diels–Alder cycloaddition reactions between a dibenzosuberenone and tetrazines that bear various substituents. The pyridazines were synthesized in high yields by oxidation of dihydropyridazine-appended dibenzosuberenones with PIFA or NO. p-Quinone derivatives of pyridazines were also obtained by H-shift isomerization following the inverse electron-demand Diels–Alder reaction of tetrazines with p-quinone dibenzosuberenone. Then these pyridazines were converted to the corresponding pyrroles by reductive treatment with zinc. It was observed that all the dihydropyridazines obtained gave absorbance and emission at long wavelengths.

Comparison of novel Ni doped exsolution perovskites as methane dry reforming catalysts

Three perovskite-type materials with a different amount of B-site Ni doping have been tested for their catalytic performance during me-thane dry reforming (MDR) followed by characterization with X-ray dif-fraction (XRD) and scanning electron microscopy (SEM). They could be activated via a reductive treatment (either during a pre-reduction step or di-rectly in reducing reaction atmosphere), the main activating mechanism be-ing the formation of Ni nanoparticles on the surface by exsolution. The catalytic activity increased with the particle size and density. The particle distribution properties could be improved by increasing the amount of Ni doping from 3 % to 10 %, by using an A-site sub-stoichiometric perovskite and by choosing a higher annealing temperature during material prepara-tion. A deactivation over time was observed, due to segregation of CaCO3 on the surface, but no coking or particle sintering occurred