Nanocrystalline corundum synthesized by ball milling of boehmite is found to be exceptionally robust toward chemical weathering, a common problem of transition aluminas in different applications, most notably in the case of supported catalysts, which are exposed to hydrothermal reaction environments. Detailed characterization and surface cation coordination analysis indicate that the absence of tetrahedral Al species on corundum makes it stable toward chemical weathering. A cobalt catalyst developed using nano-α-Al2O3 as the support showed Fischer–Tropsch synthesis activity and selectivity comparable to the benchmark Co/γ-Al2O3 and remained stable over 250 h on-stream.

Adjusting hydrocarbon product distributions in the Fischer–Tropsch (FT) synthesis is of notable significance in the context of so-called X-to-liquids (XTL) technologies. While cobalt catalysts are selective to long-chain paraffin precursors for synthetic jet- and diesel-fuels, lighter (C 10– ) alkane condensates are less valuable for fuel production. Alternatively, iron carbide-based catalysts are suitable for the coproduction of paraffinic waxes alongside liquid (and gaseous) olefin chemicals; however, their activity for the water–gas-shift reaction (WGSR) is notoriously detrimental when hydrogen-rich syngas feeds, for example, derived from (unconventional) natural gas, are to be converted. Herein the roles of pore architecture and oxide promoters of Lewis basic character on CoRu/Al 2 O 3 FT catalysts are systematically addressed, targeting the development of catalysts with unusually high selectivity to liquid olefins. Both alkali and lanthanide oxides lead to a decrease in turnover frequency . The latter, particularly PrO x , prove effective to boost the selectivity to liquid (C 5–10 ) olefins without undesired WGSR activity. In situ CO-FTIR spectroscopy suggests a dual promotion via both electronic modification of surface Co sites and the inhibition of Lewis acidity on the support, which has direct implications for double-bond isomerization reactivity and thus the regioisomery of liquid olefin products. Density functional theory calculations ascribe oxide promotion to an enhanced competitive adsorption of molecular CO versus hydrogen and olefins on oxide-decorated cobalt surfaces, dampening (secondary) olefin hydrogenation, and suggest an exacerbated metal surface carbophilicity to underlie the undesired induction of WGSR activity by strongly electron-donating alkali oxide promoters. Enhanced pore molecular transport within a multimodal meso-macroporous architecture in combination with PrO x as promoter, at an optimal surface loading of 1 Pr at nm –2 , results in an unconventional product distribution, reconciling benefits intrinsic to Co- and Fe-based FT catalysts, respectively. A chain-growth probability of 0.75, and thus >70 C% selectivity to C 5+ products, is achieved alongside lighter hydrocarbon (C 5–10 ) condensates that are significantly enriched in added-value chemicals (67 C%), predominantly α-olefins but also linear alcohols, remarkably with essentially no CO 2 side-production (<1%). Such unusual product distributions, integrating precursors for synthetic fuels and liquid platform chemicals, might be desired to diversify the scope and improve the economics of small-scale gas- and biomass-to-liquid processes.

The selective conversion of syngas to higher alcohols is an attractive albeit elusive route in the quest for effective production of chemicals from alternative carbon resources. We report the tandem integration of solid cobalt Fischer-Tropsch and molecular hydroformylation catalysts in a one-pot slurry-phase process. Unprecedented selectivities (> 50 wt %) to C 2 + alcohols are achieved at CO conversion levels > 70 %, alongside negligible CO 2 side-production. The efficient overall transformation is enabled by catalyst engineering, bridging gaps in operation temperature and intrinsic selectivity which have classically precluded integration of these reactions in a single conversion step. Swift capture of 1olefin Fischer-Tropsch primary products by the molecular hydroformylation catalyst, presumably within the pores of the solid catalyst is key for high alcohol selectivity. The results underscore that controlled cooperation between solid aggregate and soluble molecular metal catalysts, which pertain to traditionally dichotomic realms of heterogeneous and homogeneous catalysis, is a promising blueprint toward selective conversion processes.

The selective conversion of syngas to higher alcohols is an attractive albeit elusive route in the quest for effective production of chemicals from alternative carbon resources. We report the tandem integration of solid cobalt Fischer-Tropsch and molecular hydroformylation catalysts in a one-pot slurry-phase process. Unprecedented selectivities (> 50 wt %) to C 2 + alcohols are achieved at CO conversion levels > 70 %, alongside negligible CO 2 side-production. The efficient overall transformation is enabled by catalyst engineering, bridging gaps in operation temperature and intrinsic selectivity which have classically precluded integration of these reactions in a single conversion step. Swift capture of 1olefin Fischer-Tropsch primary products by the molecular hydroformylation catalyst, presumably within the pores of the solid catalyst is key for high alcohol selectivity. The results underscore that controlled cooperation between solid aggregate and soluble molecular metal catalysts, which pertain to traditionally dichotomic realms of heterogeneous and homogeneous catalysis, is a promising blueprint toward selective conversion processes.

Materials with spatially organized and multimodal porosities are very attractive in catalysis, as they can reconcile nano-confinement effects in micro-and mesopores with fast molecular transport in wide macropores. However, the associated large pore volumes often result in low overall thermal conductivities, and thus suboptimal heat management in reactions with a high thermal signature, usually with a deleterious impact on the catalytic performance. Here we report the directional freeze-casting assembly of bimodally meso-macroporous micromonolithic bodies with a hybrid backbone composed of intimately bound carbon nanotubes (CNTs) and ZrO x -Al 2 O 3 nanocrystals. A honeycomb-shaped and axially oriented macroporous architecture is achieved through the use of zirconium acetate as an ice growth modulator. (S)TEM and EDX nanospectroscopy show that the nanoscale intimacy between the CNT and oxide backbone components depends on the synthesis route of the mother slurry. As revealed by X-ray tomography, coupled to quantitative image analysis, not only the macrochannel size and wall thickness, but also the extent of axial heterogeneities in macropore diameter and spatial orientation depend on the axial temperature gradient rate during casting. The structured bodies are explored as carriers for cobalt-based catalysts for the Fischer-Tropsch production of synthetic hydrocarbons from syngas, of central significance in intensified X-to-liquid processes. Hybrid CNT-Al 2 O 3 backbone micromonolith catalysts show a high selectivity to C 3-8 olefins, owing to the fast evacuation of these primary reaction products from the metal active sites through the directional macropore system.Remarkably, the high olefin selectivity is maintained up to higher operating temperatures compared to reference catalysts based on all-oxide supports, due to a higher effective thermal conductivity which inhibits the development of hotspots under industrially relevant operating conditions. Fig. 4 Representative HAADF-STEM micrograph (top-left panel) of an ultramicrotomed cross section (150 nm nominal thickness) of a Co/CNT-ZrAlO x micromonolithic catalyst and EDX compositional maps of the same region obtained from the corresponding K-spectral lines.This journal is