Hydrodeoxygenation (HDO) is an attractive route for the upgrading of bio-oils produced from lignocellulose. Current catalysts require harsh conditions to effect HDO, decreasing the process efficiency in terms of energy and carbon balance. Herein we report a novel and facile method for synthesizing bimetallic PtCo nanoparticle catalysts (ca. 1.5 nm) highly dispersed in the framework of nitrogen-doped ordered mesoporous carbon (NOMC) for this reaction. We demonstrate that NOMC with either 2D hexagonal (p6m) or 3D cubic (Im3‾ m) structure can be easily synthesized by simply adjusting the polymerization temperature. We also demonstrate that PtCo/NOMC (metal loading: Pt 9.90 wt %; Co 3.31 wt %) is a highly effective catalyst for HDO of phenolic compounds and "real-world" biomass-derived phenolic streams. In the presence of PtCo/NOMC, full deoxygenation of phenolic compounds and a biomass-derived phenolic stream is achieved under conditions of low severity.

SummaryHerein, a lignin-centered convergent approach to produce either aliphatic or aromatic bio-hydrocarbons is introduced. First, poplar or spruce wood was deconstructed by a lignin-first biorefining process, a technique based on the early-stage catalytic conversion of lignin, yielding lignin oils along with cellulosic pulps. Next, the lignin oils were catalytically upgraded in the presence of a phosphidated Ni/SiO2 catalyst under H2 pressure. Notably, selectivity toward aliphatics or aromatics can simply be adjusted by changes in H2 pressure and temperature. The process renders two distinct main cuts of branched hydrocarbons (gasoline: C6-C10, and kerosene/diesel: C14-C20). As the approach is H2-intensive, we examined the utilization of pulp as an H2 source via gasification. For several biomass sources, the H2 obtainable by gasification stoichiometrically meets the H2 demand of the deep converting lignin-first biorefinery, making this concept plausible for the production of high-energy-density drop-in biofuels.

About 15 years ago,t he Ryoo group described the synthesis of CMK-5, am aterial consisting of ah exagonal arrangement of carbon nanotubes.E xtension of the surface casting synthesis to oxide compositions,h owever,w as not possible so far,i ns pite of many attempts.H ere it is demonstrated, that crystalline mesoporous hollow zirconia materials with very high surface areas up to 400 m 2 g À1 ,and in selected cases in the form of CMK-5-like,are indeed accessible via such as urface casting process.T he key for the successful synthesis is an increased interaction between the silica hard template surface and the zirconia precursor species by using silanol group-richm esoporous silica as ah ard template.T he surface areas of the obtained zirconias exceed those of conventionally hard-templated ones by af actor of two to three.The surface casting process seems to be applicable also to other oxide materials.High surface area, nanostructured, crystalline metal oxides are av ery interesting class of materials,d ue to their great potential in various applications. [1][2][3][4][5][6][7][8] Organic-inorganic assembly processes,using surfactants [9] or block co-polymers as soft templates,a re one feasible pathway for the creation of ordered mesoporous metal oxides. [10][11][12][13][14][15][16] Nanocasting from ordered mesoporous silica or carbon as hard template [17] is an alternative,i fs oft templating fails or only yields ill-crystallized materials.H owever,e specially the conditions for removal of the template from the pore system are problematic,s ince many oxides are reducible and/or thermally not stable,w hich can lead to collapse of the mesostructure.I n addition, without special steps the atomic scale structure stays amorphous or is only ill crystallized. Numerous attempts have been reported to enhance the stability of the framework of mesoporous metal oxides,a nd many of them are successful for selected compositions. [18][19][20][21][22] In addition, often the surface areas of the nanocast metal oxides are rather low,d ue to structural shrinkage and sintering of primary particles during the thermal treatment. Moreover,s ince the complete pore system of the mold is filled, and thus the surface area of the cast oxide corresponds to the previously exposed surface of the mold, the achievable surface area is limited. Thel atter point also prevents the synthesis of some interesting structures,such as hollow tubular arrays as in CMK-5 carbon, with very high surface areas (up to 2500 m 2 g À1 )a nd large pore volumes (up to 2.0 cm 3 g À1).[23-27] While extension to other compositions has been attempted again and again over the last 15 years,t his has not been successful so far. In the following,w ed escribe as urface-casting method for the synthesis of crystalline zirconias with very high surface areas,a nd in selected cases in form of nanotube arrays (surface cast oxide,S CO), which can be extended also to other oxides.T he process relies on as ilanol group-rich mesoporous silica as hard template,w ith as urface fu...

A simple and efficient hydrodeoxygenation strategy is described to selectively generate and separate high-value alkylphenols from pyrolysis bio-oil, produced directly from lignocellulosic biomass. The overall process is efficient and only requires low pressures of hydrogen gas (5 bar). Initially, an investigation using model compounds indicates that MoC /C is a promising catalyst for targeted hydrodeoxygenation, enabling selective retention of the desired Ar-OH substituents. By applying this procedure to pyrolysis bio-oil, the primary products (phenol/4-alkylphenols and hydrocarbons) are easily separable from each other by short-path column chromatography, serving as potential valuable feedstocks for industry. The strategy requires no prior fractionation of the lignocellulosic biomass, no further synthetic steps, and no input of additional (e.g., petrochemical) platform molecules.

We report a novel CO 2 -stable reduction-tolerant dual-phase oxygen transport membrane 40 wt% Nd 0.6 Sr 0.4 FeO 3Àd -60 wt% Ce 0.9 Nd 0.1 O 2Àd (40NSFO-60CNO), which was successfully developed by a facile one-pot EDTA-citric sol-gel method. The microstructure of the crystalline 40NSFO-60CNO phase was investigated by combined in situ X-ray diffraction (XRD), scanning electron microscopy (SEM), back scattered SEM (BSEM), and energy dispersive X-ray spectroscopy (EDXS) analyses. Oxygen permeation and long-time stability under CO 2 and CH 4 atmospheres were investigated. A stable oxygen flux of 0.21 cm 3 min À1 cm À2 at 950 C with undiluted CO 2 as sweep gas is found which is increased to 0.48 cm 3 min À1 cm À2 if the air side is coated with a porous La 0.6 Sr 0.4 CoO 3Àd (LSC) layer. All the experimental results demonstrate that the 40NSFO-60CNO not only shows good reversibility of the oxygen permeation fluxes upon temperature cycling, but also good phase stability in a CO 2 atmosphere and under the harsh conditions of partial oxidation of methane to synthesis gas up to 950 C.